Title of Invention	A PROCESS FOR POLYMERIZING OLEFINS IN THE PRESENCE OF THE CATALYST
Abstract	A method of preparing catalyst components for olefin polymerization and copolymerization The present invention relates to a method of preparing catalyst components for olefin polymerization and copolymerization wherein 2-indanone is reacted in a solvent which is dimethylformamide or tetrahydrofurane with a base which is imidazole, trithylamine or 1, 8-diazobicyclo [5.4.0] undec-7 - ene and a chlorosilane to form 2-siloxyindene according to the following reaction scheme: where R' is tert-butyl or hexyl group.

Title of Invention

A PROCESS FOR POLYMERIZING OLEFINS IN THE PRESENCE OF THE CATALYST

Abstract

A method of preparing catalyst components for olefin polymerization and copolymerization The present invention relates to a method of preparing catalyst components for olefin polymerization and copolymerization wherein 2-indanone is reacted in a solvent which is dimethylformamide or tetrahydrofurane with a base which is imidazole, trithylamine or 1, 8-diazobicyclo [5.4.0] undec-7 - ene and a chlorosilane to form 2-siloxyindene according to the following reaction scheme: where R' is tert-butyl or hexyl group.

Full Text	Heteroatora substituted metallocenfc compounds for olefin polyinerization catalyst systems and methods for preparing thereof The present invention relates to novel metallocene catalyst systems for homo- and copolymeiization of olefins, especially propylene, ethylene and higher alpha-olefins, in the presence of a cocatalyst, such as methylaluminoxane (MAO). Especially the invention relates to metallocenes with heteroatom substituted indenyl and indenyl derivative ligands, a method for tlieir preparation, and their use in polymerization of olefuis, especially propylene and ethylene. Chiral C-2 symmetric bis(indetiyl) ansa-metallocenes are precursors to highly active catalysts for stereoselective polymerization of alphaolefms. The peifonnance characteristics of these systems are different, the variations bemg induced by size and position of the substituents. E.g. dimethylsilylene bridged 2,2"-dunetliyI-4,4"-diaiyl substituted bis(iiidenyl) zirconocenes developed by Brintzinger and co¬workers (Organometallics 1994, 13, 964) and Spaleck et al, (OrganometalUcs 1994, 13, 954), produce isotactic polypropylenes witlt catalyst activities and polymer properties comparable to those obtained with heterogeneous Ziegler-Natta catalysts. The area of electronically altered bis(indenyl) metallocenes has remained relatively unexplored. Previously, it has been reported that halogen or alkoxy substitution in he in :he present invention concerns novel metallocene complexes I with en oxygen atom irectly bonded to the 2-position of a pentahapto indenyl moiety, e.g., racemic thylenebis(2-(teft-butyldimethylsiloxy)indeny()zirconium dichloride, and their app-cation in polymerization of olefms. These complexes I, in combination with MAO r oflier activators, form highly active catalyst systems for homo- and copoly-\erization of olefins. E.g., the I/MAO catalyst systems polymerizes propylene to ighly isotactic polypropylene. The propylene and ethylene polymerization activity of I/MAO exceeds those of several conventional ansa»metaIIocene/MAO catalyst systems, such as dimethylsilylenebis(4,5,6,7-tetrahydromdenyI)zirconiujn dichlo-ride/MAO, under similar polymerization conditions. The novel catalyst systems are very stable and retain their high activities at exceptionally low [Al]:[Zrl ratios. According to the invention a new catalyst precursor is obtained, in which a siloxy substitution in the 2-position of 5-membered ring of an indenyl-type compound has been carried out. Thereby it is possible to produce metallocene compounds, in which an oxygen atom is directly bonded to the 2-position of a pentahapto indenyl moiety. wherein D is one of silicon or germanium, R3, R3and R3 are the same or different and are one of a hydrogen atom, a C1-C1o hydiocarbyl group or a C1-C1o hydrocarbyloxy group, or at least two of R3, R3and R3 foim together a C2-C20 ring stmcmre; M is a transition metal of group 4 of the Periodic Table and is bound to the ligand IndY in at least an T15 bonding mode; each R is the same or different and is one of a hydrogen atom, a halogen atom, a C1 -C10 hydiocarbyl group, a C1 -C1o hydrocarbyloxy group, a tri-hydrocarbyl silyl group or two R form together a C2-C20 ring siTucture; B is a bridge atom or group between two IndY ligands or between one IndY ligand and the transition metal M; m is 1 or 2; 0 is 0 or 1; and n is 4-m when B is a bridge atom or group between two IndY ligands, or n is 4-m-o when B is a bridge atom or group between one IndY ligand and the transitioii metal M. By mono- or polysubstituted is meant that, in addition to said substituent Y, there may optionally be other substituents at the rings at said ligand IndY. By fused or non-fused is meant that any ring at said ligand IndY may be fused or non-fiisedj i.e. have at least two atoms in conmion, witihi at least one further ring. By homo- and heterocychc is meant that any ring of said ligand IndY may have only carbon ring atoms (homo- or isocyclic) or may have other ring atoms than carbon (heterocyclic). Preturately the indenyl compound according to formula (I) has the following fonnula (HI) R1 and R2 are the same or different groups selected from a hydrogen atom, a C1-C1o alkyl group, C1-C1o alkoxy group, C6-C10 aryl group, C6-C1o aiyloxy group, C2-C10 alkenyl group, C2-C10 arylalkyl group, C2-C10 allcyiaryl group, C8-C40 aiylalkenyl group or a halogen atom, preferably a C1-C1o alkyl group and/or a halogen atom. R3, R3-R6 are same or different groups selected from hydrogen, C1-C1o alkyl group, C1-C1oalkoxy group, C6-C1o aryl group, C6-C1o aiyloxy group, C2-C10 alkenyl group, C2-C1O arylalk>i group, C2-C10 alkylaiyl group, and C8-C40 arylalkenyl group. R3 and R?groups can also be connected to each other to form a ring structure and R4 may also be part of a ring structure. Preferably Mi is ziiconium. R1 and R2 are preferably the same and most preferably they are halogen atoms, for example chlorine atoms. R3 is preferably C1-ClO alkyl or aryl group and most preferably it is methyl group. R3 is likewise preferably C1-C1o alkyl or aiyl group, for example tert-butyl group, t-hexyl 3oup or cydohexyl group. Most preferably D is Si, B is -CH2CH2-, R1=R3 and is chlorine, R3 is CH3 and R5-R6 is aromatic or fiised aromatic or alkyi or hydrogen. The invention also relates to 2-trihydrocarbyl and 2-trihydiokarbyloxy siioxyindene and germyloxyindene compounds having the general formula: wherein: D is one of silicon and germanimn; R3, R3and R3 are the same or different and are one of a hydrogen atom, a C1-C1o hydrocarbyl group or a C1-C1o hydrocarbyloxy gioup, or at least two of R3, R3and R3 form together a C2-C20 ring structure; R3 is a four-atom chain forming an unsubstituted or substituted, further non-fused or further fused, homocyclic (=isocyclic) or heterocyclic, unsaturated or saturated, aliphatic or aromatic six-membered ring; and R3, R9 and Rl3 are the same or different and are one of a hydrogen atom, a C1-C1o hydrocarbyi gi"oup, a C1-C1o hydrocaibyloxy group, a tri-C1-C1o hydrocarbyl silyl group or a tri-C1-C1o hydrocarbyloxy silyl group, or one of R3 and R3 may be a bridge atom or group B to a cyclopenmdienyl, fluorenyl or indenyl group. wherein: R3, R3", R4.R6, RS3 RIO and D are the same as above; aad B is a bridge of at least one of the groups -(CH2)„-, -SiR32- or -GeR3s- whejein n is 1,8 and R3 is tlie same as above. D is preferably Si. The catalyst compounds according to the invention can be prepared from 2-tndanone. This compound can be reacted in a suitable solvent with a base and a chlorosilane to form 2-siIoxyindene with a yield of over 80 %. Suitable solvents are for example dimethylformamide (DMF) and tetrahydrofurane (THF). Suitable bases are for example imidazole, triethylamine (TEA) and l.S-diazabicyclDE5.4.0]undec-7-ene. Suitable chlorosilanes are for example tert-butyldimethylchlorosilane, t-hexyldimethylchlorosilane and cyclohexyldimethylchlorosiiane. The reaction takes place according to the following reaction scheme (VII): According to one embodiment of Hie invention 2-tert-bu1yldimethylsiloxyindene is reacted first with butyllithium and then with dimethyl dicblorosilane (Me2SiC12) to fonn dimethyisilylbis(2-teit-butyldimethylsiioxyiiidene). Butyllithium can be replaced with methyllithimn, sodium hydride or potassium hydride. Liltewise dimetliyl dicblorosilane can be replaced with any dialkyl or diaiylsilane. Silicon can be replaced with germanium. Dimethylsilylbis(2-teit-butyldimethylsiloxyindene) can be reacted with butyl-hthium, which gives the corresponding bisUthium salt. This product can be reacted with zirconium tetrachloride to yield dimethyl silylbi5(2-tert-butyldiinethylsiloxy-indenyl)zirconimn dichloride as a mixture of the racemic and meso diastereomers. ButyUifliium may be replaced as described earlier, Zirconium tetiachloride can be replaced with titanium tetrachloride or hafnium tetrachloride to give the According to another embodiment of the invention 2-teit-butyIdimethylsiloxyindene is reacted first with butyllithimn and then with dibromoethane to form bis(2-tert-butyldimethylsiloxy indenyl)etliane. This compound can be reacted with two equivalents of butylhthiuin, which gives the corresponding bislithium salt. This can then be reacted with zirconium tetrachloride to yield ethylenebis(2-tert-butyldinvethylsiloxyindenyi)zirconiura dichloiide. The lacemic diasteieamei of the latter is fonned in great excess and is easily separated from the meso isomer by fractional crystallization. Catalytic hydrogenation of racemic ethylenebis(2-tertbutyldimethylsiloxyindenyl)-zirconium dichloride yields the corresponding tetrahydroindenyl complex. The reactions takes place according to the following reaction scheme (X): In the reactions above butyllithium. may be replaced as described earlier. Zirconium tetrachloride can be replaced with titanium tetrachloride or hafiiium tetrachloride to give the corresponding titanium and hafiiium complexes. According to stiU another embodiment of the invention 2-t-hexyldimetbLyi-siloxyindene is reacted first with butyllithium and then with dibromoethane to form bis(2-t-hexyldimethy!siloxyindenyl)-ethane. This compotmd can be reacted with two equivalents of butyllithium which gives the corresponding bislithium salt This can then be reacted with with zirconium tetrachloride to yield ethylenebis(2-t- hexyldimethylsiloxymdenyDzircomum dichlonae. ihe racemic diastereomer of the Utter ,s formed in great excess and is easily separated from the meso isomer by fractional ciystalUzation. The reaction takes place according to the follo3ma reaction scheme (XI): la the reactions abov"e butylUthiura may be replaced as described earlier. Ziiconium tettachloride can be replaced with titanium tetrachloride or ha&uum tetrachloride to give the corresponding titanum and hafeium complexes. Hydrogenatioa of etili;ylenebis(2-thexyldimethylsiioxyindenyl)-2ircoraiim dichloride yields tiie corresponding tetrahydroindenyl complex niusfralive but non-limiting examples of the compounds according to the invention are, among others, 2-tert-butyldijtnelhylsiIoxyindene, 2-t-hexyldimethyl-siloxyindene, 2-cyclohexyldimetfayl-siloxyindene» 2-tett-butyIdiphenyisiloxyindene, dunethylsilylbis(2-tert-butyldunelhylsiloxyindene), diphenyUilylbis(2-tert-bu.tyldi-methylsiloxyindene, dimetliylsilylbis(2-thexyldimethylsiloxyindene), diphenyl-siIylbJs(2-thexyldimethylsiloxyindene), dimethylsilylbis(2-cyclohexyldime£hyl-siloxyindene), dipheniylsilylbis(2-cyclohexyldimethylsiloxymdene), dimethylsilyl-bis(2-tert-butyIdiphgiyU!loxyindene), diphenylsilylbis(2-tert-butyldiphenylsiloxyin-dene), racemic and meso diinethylsilylbis(2-tert-butyldiniethylsiloxyJndenyl)- zirconium dichloride, racemic and meso diphenylsilylbisC2-teit-butyldimethyl-siloxymdenyl)zirconium dichlonde, racemic and meso dimethylsilylbis(2-t-hexyl-dimethylsiioxyindenyOzirconium dichloride, racemic and meso diphenylsilyibis(2-t-hexyIdimethylsiloxyindenyl)zirconium dichloride, racemic and meso dimet-hylsilyibisC2-cyclohexyIdimethylsiloxyindenyl)z!rconium dichloride, racemic and meso dimethylsilylbisC2-cyclohexyldimethylsiloxyindenyI)zirconium dichloride, racemic and meso dimethylsilylbis(2-2-tert-butyldiphenylsiloxyindenyi)zircomum dichloride. racemic and meso diphenyIsilylbis(2-tert-butyldipheiiylsiloxy-indenyl)2irconium dichloride, racemic and meso dtmethylsilylbis(2-tert-butyl-dimethylsiloxy-4,5,6,7-tetrahydroindenyl)zirconimn dichloride, racemic and meso diphenylsiIylbis(2-tert-butyldimethylsiloxy-4,5,6,7-tetrahydroindenyl)-2irconium dichloride, racemic and meso dimethylsilylbis(2-the3cyldimethylsiloxy-4,5,6,7-tetiahydroindenyl)zircomum dichloride, racemic and meso diphenylsilylbis(2-"t-hexyldimethyl-siloxy-4,5,6,7-tetrahydroindenyl)zircomum dichloride, racemic and meso dimethylsilylbis(2-cyclohexyldimediylsiloxy-4,5,6,7-tetiiahydroindenyI)zirco-nium dichloride, racemic and meso diphenylsilylbis(2-cyciohexy!dimethylsiloxy-4,5,6,7-tetrahydroindenyl)2irconimn dichloride, racemic and meso dimethylsilylbis(2-tert-butyldiphenylsiloxy-4,5,6,7-tetraliydroindenyl)-ziJconium dichloride, racemic and meso diphenylsiIylbis(2-tert-butyldiphenylsiloxy-4,5,6,7-tetrahydroindenyOzii-conium dichloride, bis(2-teri:-butyldimethylsiloxyindenyl)-ethane, bis(2-thexyldimethyIsiIoxyindenyl)ethane, bis(2-tert-but\1diphenyl-siloxyindcnyl)ethane, bis(2-cyclohexyldimethylsiloxyindenyl)ethane, lac-ethylenebis(2-tert-butyldimethylsiloxyindenyl)zirconium dichloride, racemic and meso ethylenebis(2-t-hexyldimethylsiloxyindenyl)zirconium dichloride, racenuc and meso etiiylenebis(2-cyclohexyldimethylsiloxyindenyl)zirconium dichloride, racemic and meso ethylenebis(2-tert-butyldiphenylsiloxyindenyl)zircomum dichloride, rac-ethylenebis(2-tert-butyldimethylsiloxy-4,5,6,7-tetrahydroindenyl)-zirconium dichloride, racemic and meso ethylenebis(2-cyclohexyldimethylsiIoxy-4,5,6,7-tetrahydroindenyl)zu-conium dichloride, racemic and meso ethylenebis(2-tert-butyldiphenylsiloxy-4,5,6,7-tetraliydroindenyI)-zircommn dichloride, bis(2-t-hexyldimethylsiloxyindeny!l)ethane and rac-ethylenebis(2-t-hexyldimethylsiloxy-indenyl)zirconium dichloride. Titanium or hafiiium can be used instead of zirconium in corresponding complexes. The metallocene compounds accordmg to the invention can be used as cata3st . components for polymerization or copolymerization of olefins. The oleHns can be chosen from ethylene, propylene, butene, pentene, hexene, heptene and octene or , mixtures thereof Particularly the olefins can be selected from ethylene and propylene and mixtures thereof or together with other a-olefins. The catalysts can be either unsupported or supported. The supported catalysts are mainly used for sluny and gas phase processes. The support can be any support known for metallocene and other type catalysts. Preferable supports are silica and alumina. The compounds according to the invention can be used in combination with activator compounds, which are organometal compounds or any other compounds used in combination with metallocene compounds. Suitable activators are, for example, alumoxane compounds having the fonnula of R-(Al(R)-0)n -AIR2 where n is 1-40, m is 3-40 and R is Cl-Cg alkyl group. Preferably R is methyl group and the preferable activator is methylalumoxane (MAO). The activator can be applied according to the methods known in the art. Experimental Ml operations were carried out in argon or nitrogen atmosphere using standard Schlenk, vacuum or glove box techniques. Solvents used were dried and distilled under argon prior to use. TheH- and "C NMR spectra were recorded in CDCI3 or CD2CI2 solution using JEOL JNM"LA400 or Jeol JNM-A500 NMR spectrometer and referenced against tetramethylsilane (TMS) or the residual protons of the deuterated solvents. Direct electron ionization mass spectra (EIMS) were obtained on a Varian VG-7070E or a Vaiian-8000 mass spectrometer. Example 1 2- A solution of tert-butyldimethylchlorosilane (248.69 g, 1.65 mol) and imidazole (112.33 g, 1.65 mol) in DMF (900 mL) was reacted with 2-indanone (198.24 g, 1.50 mol) and then stirred overnight at room temperature. The reaction mixture was Heated with water (800 inL) and extracted with diethyl ether (3 3 400 mL). The combined organic phases were washed with water (2 x 400 raL) and diied over sodium sulfate. The solvents were removed under reduced pressure to leave an orange oil. Distillation under reduced pressure gave 331.2 g (89,6 %) of the title compound as s yeUow oiJ (bp 105-107 "C/O.l mbar). 3H NMR (CDCI3): d 7.19-7.07 (m, 3H); 6.97 (td, 3j = 7.3 Hz, 4j = 1,4 Hz, IH); 5.72 (dd, 4j = 1.9 Hz, 1.1 Hz, IH); 3.24 (dd, 4j « 1.7 Hz, I.I Hz, 2H); 0.96 (s. 9H); 0.23 (s, 6H). I3c NMR (CDCIs): d 162.44; 145.14; 136.53; 126.44; 123.01; 122.39; 118.92- I06.5859 46 25.59; 18.14;-4.68. Example 2 2-(t-hexvldimethvlsiloxv3mdene A solution of thexyldimethylchJorosilane (lOO.O g, 559.3 mmol) and imidazole (38.08 g, 559.3 mmol) in DMF (350 mL) was reacted with 2-ijidanone (67.40 g, 510.0 mmol) and then stiired for two days at room temperature. The reaction mixture was treated with water (300 mL). and extracted with EtzO (3 x 200 mL), The combined organic phases were washed with water (2 x 200 mL) and dried over sodium sulfate. Evaporation of the solvents left a red oil. Distillation under reduced pressure gave 116.89 g (83.5%) of the title compound as a yellow oil (bp. 128-130 T/0.4 mbar). 3H NMR (CDCI3, d): 7.24-7.10 (m, 3H); 7.00 (td, 3j = 7.3 Hz, 4j = 1.3 Hz, IH); 5.74 (d, 4j « 0.6 Hz, IH); 3.28 (s, 2H); 1.70 (sept, 3j = 6.8 Hz, IH); 0.93 (s, 6H); 0.92 (d, 3j 3 6.8 Hz, 6H); 0.29 (s, 6H). l3c NMR(CDCl3, d): 162.82; 145.71; 137.03; 126.86; 123.45; 122.73; 119.29; 106.92; 40.00; 34.49; 25.51; 20.51; 18.S9;-2.26. Example 3 2-{"c\cbhexv][dimethvl5ilox\""lindene A solution of cyclohexyldimethylchlorosilane (84.62 g, 478.7 mmol) and imidazole (32.59 g, 47S.7 mmol) in DMF (300 ml) was reacted with 2-indanone (57.62 g, 436.0 mmol). The reaction mixture was stined overnight at room tetnperature, treated with water (300 mL) and extracted with EtjO (3 x 2OO mL), The combined organic phases were washed with water (3 > 1.4 Hz, IH); 5.76 (d, 4j = 0.7 Hz, IH); 3.29 (s, 2H); 1.77-1.74 (m, 5H); 1.27-113 m 5H); 0.90 (m, IH); 0.24 (s, 6H). 13c NMR (CDCI3, d): 162.44; 145.24; 136.60; 126.47; 123.07; 122.37; 118.91; 106.32; 39.52, 27.69; 26.77; 26,46; 26.33, -3,55. Example 4 2-ftert-butvldipheHvlsUoxv3mdene To a solution of tert-butyldiphenylchlorosilane (42.43 g, 154.4 mmol) and DBU (25.64 g, 168.4 mmol) in benzene (200 mL) was added 2-mdanone (18.38 g, 139.1 mmo!) in one portion. The reaction mixture was stiired overnight, diluted with Et20 (200 mL). washed with 10% HCl (2 x 200 mL) and water (2 x 200 mL) and dried over sodium sulfate. The solvents were evaporated to leave a dark brown oil. Distillation under reduced pressiu-e gave 38,22 g (74.1%) of the title compound as a yeUow oil (bp. 172-175 "C/O.OS mbar). iH NMR (CDCI3, d): 7.77-7.74 (m, 4H): 7.46-7.36 (m. 6H); 7.18-7.16 (m, IH); 7.11-7,07 (m, IH); 6.98-6.94 (ra, 2H); 5.48 (d,J = 0.7 Hz, IH); 3.29 (s, 2H); 1.09 (s, 9H). l3C NMR (CDCI3, d): 162.13; 145.17; 136.75; 135.53; 132.43; 130.20; 127.99; 126.51; 123.15; 122.49; 119.24; 107.91; 39.43; 26.60, 19.46. Example 5 2-(teit-butvldimethylsiloxy)bisbenz[e,g]iindene To a suspension of bisbenz[e,g]-2-indanone (35.90 g, 154,5 mmol) and tert-butyldimethykhlorosilane (28,00 g, 185.5 mmol) in benzene (300 mL) was added dropwise DBU (30.60 g, 201.0 mmol) while keeping the reaction mixture cold with an icebath. Stirring was continued for 1 hour at room temperature. The organic phase was washed with water (200 mL), 5% HCl (2 x 200 mL), water (200 mJL) and dried over sodium sulfate. Evaporation of the solvents left a residue which was washed with MeOH (3 x 200 mL) to give the title compoutid (38.35 g, 110.7 mmol, 71.6%) as a slightly pink powder. EIMS (calcd/foimd): 346.1753/346.1744. 3H NMR (CDCI3, d): 8.72-8,67 (m, IH); 8.66-8.62 (m,lH); 8.02-7.96 (m. IH); 7.82-7.99 (m,lH); 7.62-7.57 (ra, 2H): 7.56-7.50 (m, IH); 7.49-7.44 (m, IH); 6.32 (m, IH); 3.73 (m, 2H); 1.03 (s, 9H); 0,33 (s, 6H). l3C NMR (CDCI3, d): 162.16, 139.79; 130.11; 129.41; 128.34; 127.73; 127.21; 126.67; 126.07; 125.53; 124,42; 123.91; 123.38; 123.24; 122.96; 104.55; 39.81; 25.68; 18.29;-4,50. Example 6 2-(tert-butyldimetfavlsiloxv")-4-7-dimethvlindene To a solution of tert-butyldimethylchlorosilane (2.85 g, 18,9 mmol) and 4,7-dimethyl-2-indanone (2.53 g, 15.8 mmol, obtained by oxidation of 4,7-3methylindene) in benzene (30 ml) was added DBU (3.13 g, 20.5 mmol) and the reaction mixture was stirred for 2 hours at room temperatuie. The mixture was diluted with Et20 (50 ml), washed with water (2 x 50 ml), 5% HCl (50 ml) water (2 X 50 ml) and dried over sodium sulphate. Evaporation of the solvents left a dark oU that was dissolved in pentane (30 ml). The unreacted starting materials were Ctystallized at -15 3C and removed by filtration. Evaporation of the solvent gave 3.03 g (69.9%) of fairly pure title compound as an orange oil. 3H NMR (CDCI3, 5): 6.94 (dq. 3J =7.7 Hz, "J=0.3 Hz, IH),; 6.7S (dq, 3J=7.7 Hz, "J=0.3 Hz, IH); 5.84 (t, "J=1 1 Hz. IH); 3.20 (m, 2H); 2.30 (s, 3H); 2.25 (s, 3H); 1.00 (s, 9H); 0.27 (s. 6H);3C N3fR (CDCI3. 6): 162,08; 143.39; 134.89; 129.45; 127.78; 125.49, 123.84: 105.28; 38.80; 25.65; 18.29; lS.21;-4.57. Example 7 Bisf 2-ftert-butvldimethvlsiIoxv V1 -indenvlkthane To a solution of 2-(tert-butyldimetiiiylsiloxy)indene (36.96 g, 150.0 mmol) b THF (150 mL) at 0 "C was added dropwise n-BuLi (60,0 mL of a 2.5 M solution in hexanes, 150.0 mmol) and die reaction mixture was stirred overnight at room temperature. The resulting solution was then cooled to -80 "C and treated dropwise with a solution of dibromoethane (14.09 g, 75.0 mmol) in THF (50 mL). After completed addition the reaction mixture was stined overnight at room temperatuie and washed with saturated ammonium cliloride solution (300 mL). Solvents from the organic phase were evaporated and the product was dissolved in Et20 (300 mL); washed with water (2 "3 200 mL) and dried over sodium sulphate. Repeated crystallizations at -15 °C afforded 22.54 g (57.9%) of the title compound as an off-white soHd. The first crystalline fraction consisted of diastereomerically pure material (Mp 108-110 °C). EMS (caicd/foimd): 518.3036/518.3028. 3H NMR (CDCI2, d, major diastereomer); 7.18-7.07 (m, 6H); 6.97 (td» 3; =: 7.4 Hz, 3} = 1.3 Hz, 2H); 5.66 (s, 2H); 3.17 (m, 2H); 1.89-1.84 (m, AA", 2H); 1.59-1.54 (m, BB", 2H); 0.94 (s, 18H); 0.23 (s, 6H); 0.21 (s, 6H). l3c NMR (CDCI3, d, major diastereoraer): 164.96; 144.39; 140.62; 126.50; 122.58; 122.41; 118.74; 104.97; 49.18: 25.67; 24.34; 18.12; -4.68; -4.88. 3H NMR (CDCI3, d, minor diastereomer): 7.17-7.05 (m, 6H); 6.97 (td, 3J =7.4 Hz, 4j = 1.2 Hz, 2H); 5.63 ($, 2H); 3.21 (m, 2H); 1.76-1.75 (m, 4H); 0.94 (s, 18H); 0.22 (s, 6H); 0.20 (s, 6H). l3c NMR (CDCIs/d, minor diastereomer): 165.18; 144.35; 140.68; 126.53; 122.71, 122.35; 118.74; 104.87; 49.04, 25.67; 25.30; 18.14, -4.77. Example 8 Bisa-ft-faexvldimethvIsiloyvjindeivvUethane To a solution of 2-(t-hexyldimethylsiloxy)indene (68.62 g, 250.0 mmoi) in THF (250 mL) at 0 "C was addsd dropwise n-BuLi (100.0 mL of a 2.5 M solution in hexanes, 250.0 nunol), and the reaction mixture was stirred overnight at room temperature. The resulting solution was then cooled to -80 "C and treated dropwise with a solution of dibromoethane (23.48 g, 125.0 nunol) in THF (100 mL). After completed addition the reaction mixtiure was stirred overnight at room tempeiatute and washed with saturated ammonium chloride solution (350 mL). Solvents from the organic phase were evaporated, and the product was dissolved in Et20 (350 mL), washed with water (2 x 300 mL) and dried over sodiimi sulphate. Repeated ciystallizations at -15 "C afforded 37.48 g (52.2%) of the title compound as off-white crystals. The first crystalline fraction consisted of diastereomerically pure material that was used for spectral characterization, EIMS (calcd/found); m/e 574.3662/574,3659. 3H NMR {CDCl-3, d): 7.22 - 7.07 (m, 6H); 6.97 (td, 3j = 7.4 Hz, 4j « 1.2 Hz, 2H); 5.65 (s, 2H); 3.15 (m, 2H); 1.91 - 1.84 (m, AA", 2H); 1.67 (sept, h = 6.8 Hz, 2H); 1.57 - 1.50 (m, BB", 2H); 0.89 (m, 24H>; 0.27 (s, 6H); 0.24 (s, 6H). 13c NMR (CDCI3, d): 164.75; 144.45; 140.58; 126.46; 122.60; 122.33; 1IS.68; 104.96; 49.24; 33.93; 25.03; 24.32; 20.14; 20.02. 18.51; 18.47; -2.66; -2.95. Example 9 Bisr2-f cyclohexvtdimethvlsiloxv)-1 -indenvDethane To an ice-cooled solution of 2-(cyclohexyldimethylsiIoxy)indefle (13.62 g, 50.0 mmol) in THF (50 mL) was added dropwise n-BiiLi (20.0 mi of a 2.5 M solution in hexanes, 50.0 mmol) and the reaction mixture was stirred ovemiglit at room temperature. The resulting solution was then cooled to -80 °C and treated diopwise with a solution of dibromoethane (4.70 g, 25.0 mmol) in THF (30 mL). The reaction mixture was gradually warmed to room temperature, stirred overnight and washed with saturated airunonium chloride solution (150 mL). The organic phase was diied over sodium sulfate. Solvents were evaporated and the remaining oil was dissolved in £t20 (100 mL). Repeated crystaUizations gave a total yield 4.03 g (28.2%) of tl\e title compound as off-white crystals. The first crystalline fraction was used for spectral characterization. EIMS (calcd/found): m/e 570.3349/570.3342. 3H NMR (CDCI3, d): 7.19 - 7.07 (m, 6H); 6.99 (td, 3j = 7.3 Hz, 3J = I.3 Hz, 2H); 5.65 (s, 2H); 3.17 (m, 2H); 1.84 - 1.79 (m, AA", 2H); 1.73 (m, lOH); 1.59 - 1.54 (ra, BB", r 2H); 1.20 (m, lOH): 0.84 (m, 2H); 0.22 (s, 6H); 0.22 (s, 6H). I3c NMR (CDCI3, d): 164.98; 144.47; 140.65; 126.51; 122.52; 122.33; U8.72; 104.64; 49 09- 27 72-26.80; 26.48; 26.37; 24.29; -3.60, Example 10 Bisf2-fteit-butvldiphenvlsiloxv1iiidenvllethane To a solution of 2-(tert-butyldiphenylsiloxy)iiidene (32.6 g, 88.0 iranol) in i"HF (200 inL) at 0 "C was added dropwise n-BuLi (35.5 mL of a 2.5 M solution in hexane, 88.8 lumol), and the reaction mixture was stured overnight at room temperature. The resulting solution was tlien cooled to -80 "C and treated dropwise with a solution of dibromoethane (8.26 g, 44.0 mmol) in THF (50 mt). The reaction mixture was gradually wanned to room temperature, stiired overnight and washed with satiu"ated ammoniura chloride solution (2 x 300 mL). The organic phase was dried over sodium sulfate. Evaporation of the solvents left a brow3 oil that was dissolved \x\ boiling Et20 (300 mL). Cooling to -15 "C gave 13.7 g (40.7%) of the title compound as a diastereomerically pure white microctystalline powder. EIMS (calcd/found): m/e 766.3662/766.3641. 1H NMR {CDCI3, d): 7.78 - 7.75 (m, 4H); 7.71 - 7.68 (m, 4H); 7.48 - 7.33 (m, 12H); 7.22 - 7.20 (m, 2H); 7.09 - 7.05 (m, 2H); 6.93 - 6.88 (m, 4H); 5.28 (s, 2H); 3.36 (m, 2H); 2.21 - 2.15 (m, AA", 2H); 1.85 -1.79 (m, BB", 2H); 1.06 (s, 18H), l3c NMR (€0013, d): 164.06; 144.19; 140.54; 135.45; 132.28; 131.91; 130.06; 129.99; 127.84; 127.79; 126.45; 122.65; 122,54; 119.06; 106.81; 49.25; 26.61; 25.10; 19.38. The mother liquor was evaporated to dryness and dissolved in boiling pentane (150 mL). Concentration and cooling to -15 °C gave the second crop 1.62 g (4.8%) of the title compound as a brown powder enriched in 3e minor diastereomer (total yield 45.5%). Example U Bis(2-ftert-butvldimethvlsiloxv3bisben2fe.g]indenvne thane To an ice-cooled solution of 2-(tert-butyldimethyIsiloxy)bisbenz[e,g]indene (20.00 %, 63,48 mmol) in THF (SO mL) was added dropwise n-BuLi (25.4 mL of a 2.5 M solution in hexanes, 63.50 mmol) and the reaction mixture stirred at room temperature for 1 hour The solvents were removed in vacuo and toluene (200 mL) was added. The resuUi:ig solution was cooled to -80 °C and dibromoethane (5.95 g, 31.67 mmol) in toluene (20 mL) was added dropwise. The reaction mixture was gradually waraied to room temperature, stirred overnight and washed with saturated ammonium chloride solution (2 x 100 mL). The organic phase was dried over sumiuii suiiatc. i3onceniration ana cooiuig to -m "L gave the title compound (900 mg, 1.25 mmol, 3.9%) as an off-white solid. EIMS (calcd/found); ra/e 718.3662/718.3659. 3H NMR (CDCh, d): 8.73-8.69 (m, 2H); 8.66 (dt, 3j = 8 2 Hz, 4j = 0.6 Hz. 2H); 8.02-7.98 (m. 2H); 7.63-7.58 (m, 6H); 7.42 (ddd, 3j = 8.2 Hz, 3j - 6.9 Hz, 4j = 1.3 Hz, 2H); 7.34 (ddd. 3j = 8.2 Hz, 3j 3 6.9 Hz, 4/ = 1.2 Hz, 2H); 6.17 (d, 4j = 0.4 Hz, 2H); 3.57-3.54 (m, 2H); 2.09-2.06 (m, 2H); J.76-1.73 (m, 2H); 0.72 (s, 18 H); O.ll (s, 6H); 0.03 (s, 6H). 13C NMR (CDC1s, d): 166.68; 139.37; 131.67; 130.32; 129.25; 127.93; 127.04; 126.70; 125.91; 125.46; 124.34; 123.61; 123.43; 123.20; 122.97; 102.67; 49,93; 25.48; 23.68; 18.04;-4.82;-5.03. Example 12 Bisri-("triinethvlsilviV2-("tert-butvldimethvlsiloxvV3-indenvnetliane To a solution of fais(2-(tert-butyldimethylsiloxy)-l-indenyl)ethane (10.38 g, 20.0 mmol) in THF (100 mL) at -20 °C was added dropwise n-BuLi (16.1 mL of a 2.5 M solution in hexane, 40.2 mmol) and the reaction mixture was stirred for 3 hours at room temperature. To the resulting solution was added dropwise chlorotrimethysilane (6.S5 g, 63.0 mmol 8.0 mL) at 0C. After completed addition the reaction mixture was stirred overnight at room temperature and the solvents were evaporated. The remaining orange solid was extracted with CH2CI2 and filtrated through celite. The solvent was evaporated and the product was dissolved in Et20 (150 mL). Concentration and cooling to 0 "C gave 10.29 g (77.6%) of a 2:1 diastereomeric mixture of the title compound as off-white crystals. EIMS (calcd/foimd): m/e 662,3827/662.3834. 3H NMR (CD2CI2, d, major/minor diastereomer): 7.51-7.49 (m, 2H, major); 7.42-7.40 (m. 2H, minor); 7.29-7.24 (m= 4+2H, major/minor): 7.22-7,17 (m. 2H, minor); 7.08-7.02 (m, 2+2H, major/minor); 3.29 (s, IH, minor); 3.27 (s, IH, major); 3.00-2.96 (m, AA", 2H, minor); 2.72-2.65 (m, AA"BB". 4H, major); 2,44-2.40 (m, BB", 2H, minor): 1.02 (s, ISH, major); 1.01 (s, 18H, minor); 0.20 (s, 6H, minor); 0.19 (s, 6H. major); 0.10 (s, 6H, minor); 0.05 (s. 6H, major); 0.02 (s, iSH, minor); 0.01 (s, ISH, major). l3C NMR (CD2CI2, d, major diastereomer); 158.32; 144.56; 139.24; 125.09; 122.74; 121.98; 119.89; 118.08; 45.08; 26.14; 24.06; 18.52; -2.39; -3.40; -4.66. 33c NMR (CDCI3, d, minof diastereomer): 158.08; 144.50; 139.14; 124.97; 122.62; 121.95; 119.95; 118.50; 45.13; 26.14; 23.86; IS.47; -2.29; -3.40; -4.24. Exapiple 13 DimethvIbisf2-(tert-butvldiinethvIsiloxvlindenvl)silaae To a solution of 2-(tert-butyldimethylsiloxy)indene (12.32 g, 50.0 mmol) in Et20 (50 mL) at 0 X was added dropwise n-BuLi (20.0 ml of a 2.5 M solution in hexane, 50.0 mmol) and the reaction mixture was stiired overnight at room temperature. The resulting solution was then added dropwise to a solution of dimethyJdichlorosilane (3.03 ml, 25.0 mmol) in Et20 (25 mL) at 0 "C The reaction mixture was stirred overnight at room temperature and washed with saturated ammonium chloride solution (150 mL), water (3 x lOO mL) and dried over sodium sulfate. Evaporation of the solvents left a red oil that was dissolved in a LI mixture of MeOH and acetone. Concentration and cooling to -30C gave 5.78 g (42.1%) of the title compound as slightly yellow crystals. The first crop consisted exclusively of the racemic diastereomer. EIMS (calcd/found): m/e 54S.2962/548.2958. Mp: 92-94 °C. iH NMR (CDCls, d); 7.22-7.14 (m. 6H); 6,98 (td, 3j =* 7.3 Hz, 4j = 1.4 Hz, 2H); 5 85 (s, 2H); 3.99 (s, 2H); 0.97 (s, 18H); 0.34 (s, 6H); 0.28 (s, 6H); -0.23 (s, 6H). 13c NMR (CDCI3, d): 164.96; 144.44; 137.55; 125.13; 122.75; 121.41; 118.83; 104.00; 43.06; 25.77; 18.20; -4.34; -4.88; -6.99. The oily residue was washed with copiously with cold MeOH (3 « 50 mL), cold pentane (50 mL) and dried in vacuo to yield 3.47 g (24.8%) of the fairly pure meso diastereomer as a red oil (total yield 66.9%). Examptg 14 Dimethvlbisf2-ft-hex\3ldimethvlsilo>cv)indenvllsilane To a solution of 2-(t-hexyldimethyUiIoxy)indene (35.58 g, 129.6 mmol) in £t20 (120 mL) at 0 "C was added dropwise n-BuLi (52.4 ml of a 2.5 M solution in hexane, 130.9 nnnol) and the reaction mixture was stin-ed ovenught at room temperature. The resulting solution was then added dropwise to a solution of dimethyldichlorosilane (7.9 mL, 64.8 mmol) in Et20 (50 mL) at 0 "C. The reaction mixture was stirred ovemiglrt at room temperature and washed with saturated ammonium chloride solution (300 mt), water (2 x 200 mL) and dried over sodium sulfate. Evaporation of the solvents left a red oil that was dissolved in a 4; 1 mixture of MeOH and acetone. Concentration and cooling to -30 "C gave 11.67 g (29.7%) of the titie compound as a white powder. The ctystalline fu"st crop consisted exclusively of the racemic diastereomer. EIMS (calcd/found); m/e 604.3588/604.3585. iR NMR (CDCI3, d): 7.22 - 7.13 (m, 6H); 6.98 (td, 3j = 7.3 Hz, "3J - 1.4 Hz, 2H); 5.85 (s, 2H); 3.99 (5, 2H); 1.72 (sept. 3j - 6,9 Hz, 2H); 0.94 (s, 6H); 0.94 (s, 6H); 0.90 (d, 3j = 6,9 Hz. 6H); 0.89 (d, 3j = 6.9 Hz, 6H); 0.38 (s, 6H): 0.34 (s, 6H); -0.23 (s, 6H). l3c NMR (CDCI3, Example 15 fBisf2-("tert-butvldimethvlsiloxv)bisbenz[e.g1indenvi")l2ircoiiiumdichloride To a solution of 2-(tert-butyldimethyisiloxy)bisbenz[e,gJindetiene (6.83 g, 19.7 mmol) in THF (50 niL) was added dropwise n-BuLi (7.9 mL of a 2.5 M solution in hexanes, 19.7 itiinol) at -20 "C. The resulting red solution was allowed to warm to room temperature and added via cannula to a solution of ZrCl4 (2,24 g, 9.6 mmol) in THF (50 mL). The reaction raixture was refluxed for 20 h. Evaporation of the THF left a solid that was extracted with CH2CI2 (50 mL) and filtrated througli celite to remove lithium chloride. Evaporation of the CH2CI2 left a red oily solid which was washed with Et20 (2 x 50 mL) to leave 2.97 g (34.0%) of the title compound as a pale green powder. Single crystals for X-ray diffraction were obtained from a concenteated toluene solution at -15 "C- In the EIMS mass spectrum of the title compound parent ions of composition C46H5oSi202ZrCl2""were observed m tlie appropriate isotope ratios at m/e = 850-859. 3H NMR (CDCI3, d): 8.45 (ra, 4H); 7.66 (m, 4H); 7.50-7.41 (m, 8H); 6.24 (s, 4H); 1.08 (s, ISH); 0.34 (sa2H). 13c NMR (CDCI3, d): 153.11; 129.88; 129-02; 128.21; 128.13; 126.95,; 126.82; 124.25; 123.37; 118.32; 97.22; 25.80; 18.48; -4.12. Example 16 rac-ethvlenebisf2-tert-butvldimethvlsiloxvindenvl)zirconiumdichloride To an ice-cooled solution of bis(2-(teTt-butyldimethyUiioxy)indenyl)ethane (5.37 g, 10.3 mmol) in THF (50 mL) was added dropwise n-BuLi {8.3 mL of a 2.5 M solution in hexanes, 20.7 mmol) and the reaction mixture was stirred overnight at room temperature. The resuhant off-yellow suspension was then added via cannula to a suspension of ZrCU (2.41 g, 10.3 mmol) in THF (20 mL) at -SO "C. The reaction mixture was gradually warmed to room temperature and stiired overnight. Evaporation of tlie solvents left a yellow solid that was exh-acted with CH2C12 (150 mL) and filtrated through celite to remove litluum chloride. Concentration and cooling to -30•€ gave 1.47 g (21.0 %) of the titie compound as a yellow tnicrociystalline solid. In the EIMS mass spectrum of the title compound parent ions of composition C32H44Si202ZrCl2"3 were observed in the appropriate isotope ratios at m/e - 676-6S4. 1H NMR (CDzCh): d 7.64 (dq, J = 8.6 Hz, 1.9 Hz, 0.9 Hz, 2H); 7.31-7.27 (m, 4H); 7.07-7.03 (m, 2H); 5.93 (d, J = 0.8 Hz. 2H); 4.01-3.90 (m, AA", 2H); 3.58-3.47 (m, BB", 2H); i.OO (s, 18H); 0.20 (s, 6H); 0.19 (s, 6H). L3c NMR (CD2CI2); d 150.12; 126.17; 125.14; 124.86; 124.79; 123.35; 116 99-108.54; 98.61; 26.30; 25.80; 18.61; -3.94; -4.27. Example !7 rac-rethvlenebisf"2-("tert-butvldi]netIiylsiioxvV4.5.6.7-tetrahvdroiTidenvli]2ircQnium dichloride A mixture of rac-[ethylenebis((2-tert-butyldimethylsiloxy)indenyl)lzirconiuin dichloride (1.00 g, 1.47 ramol) and Pt02 (20 mg) in CH2CI2 (150 mL) was hydrogenated at 70 bar in a stirred reactor for 16 h. The light green suspension was filtered through Cclite and the solvent evaporated. The residue was dissolved in hexanc (50 mt) and cooled to 0 "C to provide O.SO g (79.2""/o) of the title compound as a light green microcrystalline solid. In the EIMS mass spectrum of the title compound parent ions of composition C32H52Si2022rCl2"3 were observed at m/e « 684-692 in the appropriate isotope ratios. 3H NMR (CD2CI2, d): 5.69 (s, 2H); 3.39-3.29 (m, AA; 2H); 3,04-2.97 (m, 2H); 2.85-2.77 (ttu 2H): 2.73-2.64 (m, BB", 2H); 2.48-2.34 (m, 4H); i.90-1.70 (m, 4H); 1.59-1.42 (m, 4H); 0.92 (s, 18H); 0.20 (s, 6H);0.16(s, 6H). 13c NMR (00202, d): 142.24; 127.66; 117.29; 114,18; 106.45; 25.46; 24.46; 23.80; 22.05; 21.92; 21.75; 18.10; -4.09; -4.65. Example 18 rac-ethvlenehisC2-tert-butvldimethvlsiloxv- l-inHfinyl)hafaittm dichloride To a solution of bis(2-(tert-butyldimethylsiloxy)tQdenyl)ethane (10.38 g, 20,0 ramol) ill THF (80 mL) at 0 "C was added dropwise n-BuLi (16.1 mL of a 2.5 M solution in hexane, 40.2 mmol) and the reaction mixture was stirred overnight at room temperature. The solvents were removed in vacuo and the resulting off-white powder was mixed with HfC3 (6.41 g, 20.0 mmol). The mixture was cooled to -SO "C and precooled CH2CI2 (150 ml) was added, Th« light yellov? suspension was gradually wanned to room, temperature, stiiTed overnight and filtrated through celite to remove lithium chloride. Concentration and cooling to -30 °C gave 1.96 g (12.8%) of the title compound as a light yellow microcrystalline solid. In the EIMS mass spectrum of the title compound, parent ions of composition C32H44Si202HfCl2"were observca m me appropriate isotope ratios at m/e = 760-774. iH NMR (CD2CI2. d): 7.64 (dq, J - 8.5 Hz, 1.8 Hz. 1.0 Hz, 2H)- 7 34 - 7 25 (m, 4H); 7.05 - 7.01 (in, 2H); 5.86 (d. 4j = o.7 Hz, 2H); 4.02 - 3.92 (AA2H)-3 3.71- 3.61 (BB; 2H); 1.02 (s, 18H): 0.22 (s, 6H); 0.21 (s, 6H). 13c NMR (CD2CI2, d): 148,64; 126.19; 124.97; 124.35, 124.30; 123.49; U5.47; 105 37-96.46, 25.84; 25.52; 18.62; -3.92; -4.26, Example 19 rac-rethvlenebisf2-(t-hexvldijnethv]siloxv){ndenvl")1zirCQrutimdicliIoride To an ice-cooled solution of Ms(2-(t-hexyMimetliylsiloxy)indenyl)ethane (11-50 g, 20.0 imnol) in THF (100 mL) was added dropwise n-BuLi (16.0 mL of a 2.5 M solution in hexane, 40.0 irunol) and the reaction mixture was stiired overnight at room temperature. The resultant off-yellow suspension was then added via cannula to a suspension of ZrCU (4.66 g, 20.0 irnnol) in THF (25 mL) at -80 "C. Tiie reaction mixture was gradually wanned to room temperature and stirred overnight. Evaporationoftliesolventsleftayellowsolid that was extracted with CH2CI2 (150 mL) and filtrated through C6lite to remove lithium chloride. Concentration and cooling to -30 "C gave 3.25 g (22.1 %) of the title compound as a yellow raicrociystalline solid. Single crystals for X-ray dif&action were obtained from a saturated toluene solution at ambient temperature. In the EIMS mass spectrum of the title compoimd parent ions of composition C35H52Si202ZrCl2"were observed in the appropriate isotope ratios at m,"e = 732-740, 3H NMR (CDoCl3, d): 7.66 (dq, J = 8.6 Hz, 1.8 Hz, 1.0 Hz, 2H); 7.35 - 7,29 (m. 4H); 7,08 - 7.04 (m, 2H), 5.95 (d, 4j = 0.6 Hz, 2H); 4.04 - 3.94 (m, AA". 2H); 3.56 - 3.46 (m, BB", 2H); 1-74 (sept. 3j = 6.8 Hz, 2H); 0.99 (s, 6H); 0.97 (s, 6H); 0.95 (d, 3j - 6.8 Hz, 6H); 0.94 (d, 3j :. 6.8 Hz, 6H); 0.26 (s, 6H); 0.25 (s. 6H). 33c NNIR (00202, d): 150.48; 126.13; 125.18; 125.10; 124.85; 123.32; 116.94; 98.53; 34.22; 26,41; 25.84; 20.35; 20.14; 18.80; 18.64;-1.62;-2.01 Example 20 rac- and masn-(limethvlsilvlenebisf2-tert-butvldimethylsiloxvindenvl")zirconxum iichlorides To a solution of dimethylbis(2-(tert-butyIdimethyIsiloxy)indenyl)silane (10.98 g, >0,0 mmol) in Et20 (40 mL) at 0 ""C was added dropwise n-BuLi (16.0 mL of a 2.5 vl solution in hexane, 40.0 mmol) and the reaction mixture was stirred oveinight at 00m temperature. The solvents were removed in vacuo to leave an off-white powder that was mixed with ZrCU (4.66 g, 20 mraol). The mixture was cooled to -80 °C and preceded CH2CI2 (150 ml) was added. The liglit yellow suspension was gradually wanned to room temperature, stirred overnight and filtrated through celite 3 to remove lithium chloride. Concentration and cooling to -30C gave 7.95 g (56.0%) of an approximately 2:1 rac/meso mixture of the fairly pure title compound as a bright yellow powder. In the ElMS mass spectrum of the title compound, parent ions of composition C32H46Si302ZrCl2"were observed in tiie appropriate isotope ratios at m/e 706-714. Small amounts of the fairly pure rac diastereomer of the tide compound were obtained by carrying out the reaction in THF solution, foUowed by removal of LiCl and ciystallization from Et20.H HMR (CD2CI2, d, rac): 7.47-7.44 (m, 2H); 1.7>1"1.H (m, 4H); 6.91-6.87 (m, 2H); 6.22 (d, "3J = 0.8 Hz, 2H); 1.19 (s,6H); 0.92 (s, 18H); 0.27 (s, en); 0.21 (s, 6H). l3c NMR (CDsC1a, d, rac); 155.89; 128.69; 127.13; 126.84; 125.07; 124.94; U9.69; 104.50; 73.22; 26.12; 19.23. 1.04;-3,36;-3.S7. POLYMERIZATION TESTS Example 21 The polymerizations were perfonned in a 0.5 1 Biichi glass autoclave m 200 ml of toluene. In a typical run half of the MAO/toluene solution was added to the reactor and stirred for 5 minutes in order to reduce any impurities in the reactor. In a parallel procedure 10-15 pmmol of the metallocene was dissolved in the remaining half of the MAO/toluene solution and preactivated at 25C for 5 min. The catalyst/activatoE mixture was charged into tlie reactor and the polymerization was started by introducing tiie olefin monomer. The polymerization was interrupted after 20 or 60 minutes by addition of ethanol or methanol. The polymer was analyzed after being washed with etbanoI/HCl or methanol/HCl. Vlethylaluminoxane (R-VO) was used as 29.3 w-% toluene solution (Al total 13.1 % "/o w/w, Ai as TMA 3.50 % w/w). High purity ethylene and propylene (99,5 %) vere used as monomers. :he results are presented in tlie Table 1 below. Example 33 The polyraerization with the fmetalioceneJ3[B(C6F6)4r catalyst system were cairied out at -20C and 2.0 bai propylene pressure using triethylalumina (TEA) as impttrity scavenger. In a typical run 0.3 g of TEA was stirred with 50 ml of toluene followed by the addition of 5 umol of the metallocene. The cation forming agent (14 Minol) was added via a syringe. The polyraerization was interrupted after 60 min by addition of ethanol or methanol. The polymer was analyzed after being washed with ethanol/HCl or methanoI/HCl. WE CLAIM: 1. A method of preparing catalyst components for olefin polymerization and copolymerization wherein 2-indanone is reacted in a solvent which is dimethylformamide or tetrahydrofurane with a base which is imidazole, trithylamine or 1, 8-diazobicyclo [5.4,0] undec-7 - ene and a chlorosilane to form 2-siloxyjndene according to the following reaction scheme: 2. The method according to claim 1, wherein the base is selected from imidazole and triethylamine (TEA) and chlorosilanes are selected from tert- butyldimethylchlorosilane, t-hexyldimethylchlorosilane and cyclohexyldimethyl- chlorosilane. 3. The method according to claims 1 or 2, wherein the reaction is continued according to the following reaction scheme: 4. The method according to claims 1 or 2, wherein the reaction is continued according to the following reaction scheme (X): 5. The method according to claims 1 or 2, wherein the reaction is continued according to the following reaction scheme: 6. A process for polymerizing olefins wherein one or more olefin selected fiom ethylene, propylene, hutylene, pentene, hexane, heptene and octene is/are contacted under polymerization conditions in the presence of the catalyst prepared by the process as claimed in any one of the preceding claims, the said catalyst comprising a catalyst precursor having the formula wherein: each IndY is the same or different and is one of a mono- or polysubstituted, fused or non-fused, homo- or heterocyclic indenyl ligand, dihydroindenyl ligand or tetrahydroindenyl ligand, which ligand is substituted at the 2-position of its indenyl structure by the group Y, which group Y has the following structure (II): wherein D is one of silicon or gennanium, R3 R3 and R4 are the same or different and are one of a hydrogen atom, a C1-C10 hydrocarbyl group or a C1-C10 hydro- carbyloxy group, or at least two of R3 R3 and R4 form together a C2-C20 ring structure; M is a transition metal of group 4 of the Periodic Table and is bound to the ligand IndY in at least an ri5 bonding mode; each R is the same or different and is one of a hydrogen atom, a halogen atom, a C1-C10 hydrocarbyl group, a C1-C10 hydrocarbyloxy group, a tri-hydrocarbyl silyl group or two R form together a C2-C20 ring structure; B is a bridge atom or group between two IndY ligands or between one IndY ligand and the transition metal M; m is 1 or 2; o is 0 or 1; and n is 4-m when B is a bridge atom or group between two IndY ligands, or n is 4-m-o when B is a bridge atom or group between one IndY ligand and the transition metal M. 7. The process according to claim 6, wherein said catalyst precursor has the formula III; where M is a metal selected from zirconium, titanium or hafiiium, D is an element selected from silicon (Si) or germanium (Ge), B is a bridge comprising at least one of-(CH 2 )n, ~Si(R. 3)2- or -Ge(R3)2-, wherein n = 1-8 , R1 and R2 are the same or different groups selected from hydrogen, C1-C1o alkyl group, C1-C10 alkoxy group, C6-C10 aryl group, C6-C10 aryloxy group, C2-C,oalkenyl group, C2-C10 aryl alkyl group, C2-C10 alkyl aryl group, Cg-C40 arylalkenyl group or a halogen atom, R3, R3-R6 are the same or different group selected from hydrogen, C1-C1o alkyl group, C1-C10 alkoxy group, C6-C10 aryl group, Cg-C10 aryloxy group, C2-C10 alkenyl group, C7-C22 arylalkyl group, C7-C22 alkyl aryl group, and C8-C40 arylarkenyl group. R3 and R3 -groups can also be connected to each other to form a ring structure and R4 may also be a ring structure. 8. The process according to claim 6 or 7, wherein M is zirconium and D is silicon. 9. The process according to claim 7, wherein R1 and R2 are preferably the same and most preferably they are halogen atoms, preferably chlorine atoms. 10. The process according to any one of claims 7 to 9, wherein R3 and/or R3 is C1-C10 alkyl or aryl group and most preferably methyl group and R 4 is C1-C10 alkyl or aryl group, preferably tert-butyl group, t-hexyl group or cyclohexyl group. 11. The process according to any one of claims 7 to 10, wherein D is Si, B is -CH 2CH 2-, R=R=R2 and is chlorine, R3 is CH3 and R5-R6 is aromatic or fused aromatic or alkyl or hydrogen. 12. The process according to any one of claims 7 to 11, wherein said catalyst precursor is based on a 2 tri-hydrocarbyl siloxy indene, 2-tri-hydrocarbyloxy siloxy indene, 2-tri- hydrocarbyloxy germyloxy indene or 2-tri-hydrocarbyloxy germyloxy indene compound having the general formula: wherein D is one of silicon and germanium; R3 R3 and R4 are the same or different and are one of a hydrogen atom, a C1-C10 hydrocarbyl group or a C1-C1o hydrocarbyloxy group, or at least two of R3 R3 and R4 form together a C2-C20 ring structure; R3 is a four-atom chain forming an unsubstituted or substituted, further non-fused or further fused, homocyclic (=isocyclic) or heterocyclic, unsaturated or saturated, aliphatic or aromatic six-membered ring M and R3, R and R10 are the same or different and are one of a hydrogen atom, a C1-C10 hydrocarbyl group, a C1-C10 hydrocarbyloxy group, a tri-C1-C10 hydrocarbyl silyl group or a tri- C1-C\o hydrocarbyloxy silyl group, or one of R3 and R3 may be a bridge atom or group B to a cyclopentadienyl; fluorenyl or indenyl group. 13. The process according to claim 12, wherein 2-tri-hydrocarbylsiloxy indene or 2- tri-hydrocarbylgermyloxy indene has the following formula: wherein: R3, R 3 -R3 ars the same or dififerent and are one of a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C10aryl group, a C1-C10 alkenyl group, a C7-C22 aiylalkyl group, a C7-C22 alkylaryl group, or a Cg-C23 arylalkenyl group, or at least two of R\ R3 and R"* form together a C2-C10 ring structure, and R 3 R 3 and R3** are the same as above. 14. The process according to claims 12 or 13 wherein 2-tri-hydrocarbylsiloxy indene or 2-tri-hydrocarbylgermyloxy indene has the general formula (VI) wherein: R3 R3, R4 - R3 R3 R° and D are the same as above; and B is a bridge of at least one of the groups -{CH2)n-, -SiR \- or -GeR 32-, wherein n is 1-8 and R3 is the same as above. 10. the processaccording to any one of claims 12 to 9, wherein 2-tri-hydrocarbylsiloxy indene or 2-tri-hydrDcarbylgermyloxy indene D is silicon. 16. A method of preparing catalyst components for olefin polymerization substantially as herein described and exemplified. 17. A process for polymerizing olefins in the presence of a catalyst substantially as herein described and exemplified.

Full Text

Heteroatora substituted metallocenfc compounds for olefin polyinerization catalyst systems and methods for preparing thereof
The present invention relates to novel metallocene catalyst systems for homo- and copolymeiization of olefins, especially propylene, ethylene and higher alpha-olefins, in the presence of a cocatalyst, such as methylaluminoxane (MAO). Especially the invention relates to metallocenes with heteroatom substituted indenyl and indenyl derivative ligands, a method for tlieir preparation, and their use in polymerization of olefuis, especially propylene and ethylene.
Chiral C-2 symmetric bis(indetiyl) ansa-metallocenes are precursors to highly active catalysts for stereoselective polymerization of alphaolefms. The peifonnance characteristics of these systems are different, the variations bemg induced by size and position of the substituents. E.g. dimethylsilylene bridged 2,2"-dunetliyI-4,4"-diaiyl substituted bis(iiidenyl) zirconocenes developed by Brintzinger and co¬workers (Organometallics 1994, 13, 964) and Spaleck et al, (OrganometalUcs 1994, 13, 954), produce isotactic polypropylenes witlt catalyst activities and polymer properties comparable to those obtained with heterogeneous Ziegler-Natta catalysts.
The area of electronically altered bis(indenyl) metallocenes has remained relatively unexplored. Previously, it has been reported that halogen or alkoxy substitution in he in :he present invention concerns novel metallocene complexes I with en oxygen atom irectly bonded to the 2-position of a pentahapto indenyl moiety, e.g., racemic thylenebis(2-(teft-butyldimethylsiloxy)indeny()zirconium dichloride, and their app-cation in polymerization of olefms. These complexes I, in combination with MAO r oflier activators, form highly active catalyst systems for homo- and copoly-\erization of olefins. E.g., the I/MAO catalyst systems polymerizes propylene to ighly isotactic polypropylene. The propylene and ethylene polymerization activity

of I/MAO exceeds those of several conventional ansa»metaIIocene/MAO catalyst systems, such as dimethylsilylenebis(4,5,6,7-tetrahydromdenyI)zirconiujn dichlo-ride/MAO, under similar polymerization conditions. The novel catalyst systems are very stable and retain their high activities at exceptionally low [Al]:[Zrl ratios.
According to the invention a new catalyst precursor is obtained, in which a siloxy substitution in the 2-position of 5-membered ring of an indenyl-type compound has been carried out. Thereby it is possible to produce metallocene compounds, in which an oxygen atom is directly bonded to the 2-position of a pentahapto indenyl moiety.

wherein D is one of silicon or germanium, R3, R3and R3 are the same or different and are one of a hydrogen atom, a C1-C1o hydiocarbyl group or a C1-C1o hydrocarbyloxy group, or at least two of R3, R3and R3 foim together a C2-C20 ring stmcmre; M is a transition metal of group 4 of the Periodic Table and is bound to the ligand IndY in at least an T15 bonding mode; each R is the same or different and is one of a hydrogen atom, a halogen atom, a C1 -C10 hydiocarbyl group, a C1 -C1o hydrocarbyloxy group, a tri-hydrocarbyl silyl group or two R form together a C2-C20 ring siTucture; B is a bridge atom or group between two IndY ligands or between one IndY ligand and the transition metal M; m is 1 or 2; 0 is 0 or 1; and n is 4-m when B is a bridge atom or group between two IndY ligands, or n is 4-m-o

when B is a bridge atom or group between one IndY ligand and the transitioii metal M.
By mono- or polysubstituted is meant that, in addition to said substituent Y, there may optionally be other substituents at the rings at said ligand IndY.
By fused or non-fused is meant that any ring at said ligand IndY may be fused or non-fiisedj i.e. have at least two atoms in conmion, witihi at least one further ring.
By homo- and heterocychc is meant that any ring of said ligand IndY may have only carbon ring atoms (homo- or isocyclic) or may have other ring atoms than carbon (heterocyclic).
Preturately the indenyl compound according to formula (I) has the following fonnula (HI)

R1 and R2 are the same or different groups selected from a hydrogen atom, a C1-C1o alkyl group, C1-C1o alkoxy group, C6-C10 aryl group, C6-C1o aiyloxy group, C2-C10 alkenyl group, C2-C10 arylalkyl group, C2-C10 allcyiaryl group, C8-C40 aiylalkenyl group or a halogen atom, preferably a C1-C1o alkyl group and/or a halogen atom.
R3, R3-R6 are same or different groups selected from hydrogen, C1-C1o alkyl group, C1-C1oalkoxy group, C6-C1o aryl group, C6-C1o aiyloxy group, C2-C10 alkenyl group, C2-C1O arylalk>i group, C2-C10 alkylaiyl group, and C8-C40 arylalkenyl group. R3 and R?groups can also be connected to each other to form a ring structure and R4 may also be part of a ring structure.
Preferably Mi is ziiconium.
R1 and R2 are preferably the same and most preferably they are halogen atoms, for example chlorine atoms.
R3 is preferably C1-ClO alkyl or aryl group and most preferably it is methyl group. R*3 is likewise preferably C1-C1o alkyl or aiyl group, for example tert-butyl group, t-hexyl 3oup or cydohexyl group.
Most preferably D is Si, B is -CH2CH2-, R1=R3 and is chlorine, R3 is CH3 and R5-R6 is aromatic or fiised aromatic or alkyi or hydrogen.
The invention also relates to 2-trihydrocarbyl and 2-trihydiokarbyloxy siioxyindene and germyloxyindene compounds having the general formula:
wherein: D is one of silicon and germanimn; R3, R3and R*3 are the same or different and are one of a hydrogen atom, a C1-C1o hydrocarbyl group or a C1-C1o hydrocarbyloxy gioup, or at least two of R3, R3and R3 form together a C2-C20

ring structure; R3 is a four-atom chain forming an unsubstituted or substituted, further non-fused or further fused, homocyclic (=isocyclic) or heterocyclic, unsaturated or saturated, aliphatic or aromatic six-membered ring; and R3, R9 and Rl3 are the same or different and are one of a hydrogen atom, a C1-C1o hydrocarbyi gi"oup, a C1-C1o hydrocaibyloxy group, a tri-C1-C1o hydrocarbyl silyl group or a tri-C1-C1o hydrocarbyloxy silyl group, or one of R3 and R3 may be a bridge atom or group B to a cyclopenmdienyl, fluorenyl or indenyl group.

wherein: R3, R3", R4.R6, RS3 RIO and D are the same as above; aad B is a bridge of at least one of the groups -(CH2)„-, -SiR32- or -GeR3s- whejein n is 1,8 and R3 is tlie same as above. D is preferably Si.
The catalyst compounds according to the invention can be prepared from 2-tndanone. This compound can be reacted in a suitable solvent with a base and a chlorosilane to form 2-siIoxyindene with a yield of over 80 %. Suitable solvents are for example dimethylformamide (DMF) and tetrahydrofurane (THF). Suitable bases are for example imidazole, triethylamine (TEA) and l.S-diazabicyclDE5.4.0]undec-7-ene. Suitable chlorosilanes are for example tert-butyldimethylchlorosilane, t-hexyldimethylchlorosilane and cyclohexyldimethylchlorosiiane. The reaction takes place according to the following reaction scheme (VII):

According to one embodiment of Hie invention 2-tert-bu1yldimethylsiloxyindene is reacted first with butyllithium and then with dimethyl dicblorosilane (Me2SiC12) to fonn dimethyisilylbis(2-teit-butyldimethylsiioxyiiidene). Butyllithium can be replaced with methyllithimn, sodium hydride or potassium hydride. Liltewise dimetliyl dicblorosilane can be replaced with any dialkyl or diaiylsilane. Silicon can be replaced with germanium.
Dimethylsilylbis(2-teit-butyldimethylsiloxyindene) can be reacted with butyl-hthium, which gives the corresponding bisUthium salt. This product can be reacted with zirconium tetrachloride to yield dimethyl silylbi5(2-tert-butyldiinethylsiloxy-indenyl)zirconimn dichloride as a mixture of the racemic and meso diastereomers. ButyUifliium may be replaced as described earlier, Zirconium tetiachloride can be replaced with titanium tetrachloride or hafnium tetrachloride to give the

According to another embodiment of the invention 2-teit-butyIdimethylsiloxyindene is reacted first with butyllithimn and then with dibromoethane to form bis(2-tert-butyldimethylsiloxy indenyl)etliane. This compound can be reacted with two equivalents of butylhthiuin, which gives the corresponding bislithium salt. This can then be reacted with zirconium tetrachloride to yield ethylenebis(2-tert-butyldinvethylsiloxyindenyi)zirconiura dichloiide. The lacemic diasteieamei of the latter is fonned in great excess and is easily separated from the meso isomer by fractional crystallization. Catalytic hydrogenation of racemic ethylenebis(2-tertbutyldimethylsiloxyindenyl)-zirconium dichloride yields the corresponding tetrahydroindenyl complex. The reactions takes place according to the following reaction scheme (X):

In the reactions above butyllithium. may be replaced as described earlier. Zirconium tetrachloride can be replaced with titanium tetrachloride or hafiiium tetrachloride to give the corresponding titanium and hafiiium complexes.
According to stiU another embodiment of the invention 2-t-hexyldimetbLyi-siloxyindene is reacted first with butyllithium and then with dibromoethane to form bis(2-t-hexyldimethy!siloxyindenyl)-ethane. This compotmd can be reacted with two equivalents of butyllithium which gives the corresponding bislithium salt This can then be reacted with with zirconium tetrachloride to yield ethylenebis(2-t-

hexyldimethylsiloxymdenyDzircomum dichlonae. ihe racemic diastereomer of the Utter ,s formed in great excess and is easily separated from the meso isomer by fractional ciystalUzation. The reaction takes place according to the follo3ma reaction scheme (XI):

la the reactions abov"e butylUthiura may be replaced as described earlier. Ziiconium tettachloride can be replaced with titanium tetrachloride or ha&uum tetrachloride to give the corresponding titanum and hafeium complexes. Hydrogenatioa of etili;ylenebis(2-thexyldimethylsiioxyindenyl)-2ircoraiim dichloride yields tiie corresponding tetrahydroindenyl complex
niusfralive but non-limiting examples of the compounds according to the invention are, among others, 2-tert-butyldijtnelhylsiIoxyindene, 2-t-hexyldimethyl-siloxyindene, 2-cyclohexyldimetfayl-siloxyindene» 2-tett-butyIdiphenyisiloxyindene, dunethylsilylbis(2-tert-butyldunelhylsiloxyindene), diphenyUilylbis(2-tert-bu.tyldi-methylsiloxyindene, dimetliylsilylbis(2-thexyldimethylsiloxyindene), diphenyl-siIylbJs(2-thexyldimethylsiloxyindene), dimethylsilylbis(2-cyclohexyldime£hyl-siloxyindene), dipheniylsilylbis(2-cyclohexyldimethylsiloxymdene), dimethylsilyl-bis(2-tert-butyIdiphgiyU!loxyindene), diphenylsilylbis(2-tert-butyldiphenylsiloxyin-dene), racemic and meso diinethylsilylbis(2-tert-butyldiniethylsiloxyJndenyl)-

zirconium dichloride, racemic and meso diphenylsilylbisC2-teit-butyldimethyl-siloxymdenyl)zirconium dichlonde, racemic and meso dimethylsilylbis(2-t-hexyl-dimethylsiioxyindenyOzirconium dichloride, racemic and meso diphenylsilyibis(2-t-hexyIdimethylsiloxyindenyl)zirconium dichloride, racemic and meso dimet-hylsilyibisC2-cyclohexyIdimethylsiloxyindenyl)z!rconium dichloride, racemic and meso dimethylsilylbisC2-cyclohexyldimethylsiloxyindenyI)zirconium dichloride, racemic and meso dimethylsilylbis(2-2-tert-butyldiphenylsiloxyindenyi)zircomum dichloride. racemic and meso diphenyIsilylbis(2-tert-butyldipheiiylsiloxy-indenyl)2irconium dichloride, racemic and meso dtmethylsilylbis(2-tert-butyl-dimethylsiloxy-4,5,6,7-tetrahydroindenyl)zirconimn dichloride, racemic and meso diphenylsiIylbis(2-tert-butyldimethylsiloxy-4,5,6,7-tetrahydroindenyl)-2irconium dichloride, racemic and meso dimethylsilylbis(2-the3cyldimethylsiloxy-4,5,6,7-tetiahydroindenyl)zircomum dichloride, racemic and meso diphenylsilylbis(2-"t-hexyldimethyl-siloxy-4,5,6,7-tetrahydroindenyl)zircomum dichloride, racemic and meso dimethylsilylbis(2-cyclohexyldimediylsiloxy-4,5,6,7-tetiiahydroindenyI)zirco-nium dichloride, racemic and meso diphenylsilylbis(2-cyciohexy!dimethylsiloxy-4,5,6,7-tetrahydroindenyl)2irconimn dichloride, racemic and meso dimethylsilylbis(2-tert-butyldiphenylsiloxy-4,5,6,7-tetraliydroindenyl)-ziJconium dichloride, racemic and meso diphenylsiIylbis(2-tert-butyldiphenylsiloxy-4,5,6,7-tetrahydroindenyOzii-conium dichloride, bis(2-teri:-butyldimethylsiloxyindenyl)-ethane, bis(2-thexyldimethyIsiIoxyindenyl)ethane, bis(2-tert-but\1diphenyl-siloxyindcnyl)ethane, bis(2-cyclohexyldimethylsiloxyindenyl)ethane, lac-ethylenebis(2-tert-butyldimethylsiloxyindenyl)zirconium dichloride, racemic and meso ethylenebis(2-t-hexyldimethylsiloxyindenyl)zirconium dichloride, racenuc and meso etiiylenebis(2-cyclohexyldimethylsiloxyindenyl)zirconium dichloride, racemic and meso ethylenebis(2-tert-butyldiphenylsiloxyindenyl)zircomum dichloride, rac-ethylenebis(2-tert-butyldimethylsiloxy-4,5,6,7-tetrahydroindenyl)-zirconium dichloride, racemic and meso ethylenebis(2-cyclohexyldimethylsiIoxy-4,5,6,7-tetrahydroindenyl)zu-conium dichloride, racemic and meso ethylenebis(2-tert-butyldiphenylsiloxy-4,5,6,7-tetraliydroindenyI)-zircommn dichloride, bis(2-t-hexyldimethylsiloxyindeny!l)ethane and rac-ethylenebis(2-t-hexyldimethylsiloxy-indenyl)zirconium dichloride. Titanium or hafiiium can be used instead of zirconium in corresponding complexes.
The metallocene compounds accordmg to the invention can be used as cata3st . components for polymerization or copolymerization of olefins. The oleHns can be chosen from ethylene, propylene, butene, pentene, hexene, heptene and octene or ,

mixtures thereof Particularly the olefins can be selected from ethylene and propylene and mixtures thereof or together with other a-olefins.
The catalysts can be either unsupported or supported. The supported catalysts are mainly used for sluny and gas phase processes. The support can be any support known for metallocene and other type catalysts. Preferable supports are silica and alumina.
The compounds according to the invention can be used in combination with activator compounds, which are organometal compounds or any other compounds used in combination with metallocene compounds. Suitable activators are, for example, alumoxane compounds having the fonnula of R-(Al(R)-0)n -AIR2 where n is 1-40, m is 3-40 and R is Cl-Cg alkyl group. Preferably R is methyl group and the preferable activator is methylalumoxane (MAO). The activator can be applied according to the methods known in the art.
Experimental
Ml operations were carried out in argon or nitrogen atmosphere using standard Schlenk, vacuum or glove box techniques. Solvents used were dried and distilled under argon prior to use. TheH- and "*C NMR spectra were recorded in CDCI3 or CD2CI2 solution using JEOL JNM"LA400 or Jeol JNM-A500 NMR spectrometer and referenced against tetramethylsilane (TMS) or the residual protons of the deuterated solvents. Direct electron ionization mass spectra (EIMS) were obtained on a Varian VG-7070E or a Vaiian-8000 mass spectrometer.
Example 1 2- A solution of tert-butyldimethylchlorosilane (248.69 g, 1.65 mol) and imidazole (112.33 g, 1.65 mol) in DMF (900 mL) was reacted with 2-indanone (198.24 g, 1.50 mol) and then stirred overnight at room temperature. The reaction mixture was Heated with water (800 inL) and extracted with diethyl ether (3 3 400 mL). The combined organic phases were washed with water (2 x 400 raL) and diied over sodium sulfate. The solvents were removed under reduced pressure to leave an orange oil. Distillation under reduced pressure gave 331.2 g (89,6 %) of the title compound as s yeUow oiJ (bp 105-107 "C/O.l mbar). 3H NMR (CDCI3): d 7.19-7.07 (m, 3H); 6.97 (td, 3j = 7.3 Hz, 4j = 1,4 Hz, IH); 5.72 (dd, 4j = 1.9 Hz, 1.1 Hz,

IH); 3.24 (dd, 4j « 1.7 Hz, I.I Hz, 2H); 0.96 (s. 9H); 0.23 (s, 6H). I3c NMR (CDCIs): d 162.44; 145.14; 136.53; 126.44; 123.01; 122.39; 118.92- I06.5859 46 25.59; 18.14;-4.68.
Example 2 2-(t-hexvldimethvlsiloxv3mdene
A solution of thexyldimethylchJorosilane (lOO.O g, 559.3 mmol) and imidazole (38.08 g, 559.3 mmol) in DMF (350 mL) was reacted with 2-ijidanone (67.40 g, 510.0 mmol) and then stiired for two days at room temperature. The reaction mixture was treated with water (300 mL). and extracted with EtzO (3 x 200 mL), The combined organic phases were washed with water (2 x 200 mL) and dried over sodium sulfate. Evaporation of the solvents left a red oil. Distillation under reduced pressure gave 116.89 g (83.5%) of the title compound as a yellow oil (bp. 128-130 T/0.4 mbar). 3H NMR (CDCI3, d): 7.24-7.10 (m, 3H); 7.00 (td, 3j = 7.3 Hz, 4j =
1.3 Hz, IH); 5.74 (d, 4j « 0.6 Hz, IH); 3.28 (s, 2H); 1.70 (sept, 3j = 6.8 Hz, IH);
0.93 (s, 6H); 0.92 (d, 3j 3 6.8 Hz, 6H); 0.29 (s, 6H). l3c NMR(CDCl3, d): 162.82;
145.71; 137.03; 126.86; 123.45; 122.73; 119.29; 106.92; 40.00; 34.49; 25.51;
20.51; 18.S9;-2.26.
Example 3 2-{"c\cbhexv][dimethvl5ilox\""lindene
A solution of cyclohexyldimethylchlorosilane (84.62 g, 478.7 mmol) and imidazole (32.59 g, 47S.7 mmol) in DMF (300 ml) was reacted with 2-indanone (57.62 g, 436.0 mmol). The reaction mixture was stined overnight at room tetnperature, treated with water (300 mL) and extracted with EtjO (3 x 2OO mL), The combined organic phases were washed with water (3 > 1.4 Hz, IH); 5.76 (d, 4j = 0.7 Hz, IH); 3.29 (s, 2H); 1.77-1.74 (m, 5H); 1.27-113
m 5H); 0.90 (m, IH); 0.24 (s, 6H). 13c NMR (CDCI3, d): 162.44; 145.24; 136.60;
126.47; 123.07; 122.37; 118.91; 106.32; 39.52, 27.69; 26.77; 26,46; 26.33, -3,55.

Example 4 2-ftert-butvldipheHvlsUoxv3mdene
To a solution of tert-butyldiphenylchlorosilane (42.43 g, 154.4 mmol) and DBU (25.64 g, 168.4 mmol) in benzene (200 mL) was added 2-mdanone (18.38 g, 139.1 mmo!) in one portion. The reaction mixture was stiired overnight, diluted with Et20 (200 mL). washed with 10% HCl (2 x 200 mL) and water (2 x 200 mL) and dried over sodium sulfate. The solvents were evaporated to leave a dark brown oil. Distillation under reduced pressiu-e gave 38,22 g (74.1%) of the title compound as a yeUow oil (bp. 172-175 "C/O.OS mbar). iH NMR (CDCI3, d): 7.77-7.74 (m, 4H): 7.46-7.36 (m. 6H); 7.18-7.16 (m, IH); 7.11-7,07 (m, IH); 6.98-6.94 (ra, 2H); 5.48 (d,J = 0.7 Hz, IH); 3.29 (s, 2H); 1.09 (s, 9H). l3C NMR (CDCI3, d): 162.13; 145.17; 136.75; 135.53; 132.43; 130.20; 127.99; 126.51; 123.15; 122.49; 119.24; 107.91; 39.43; 26.60, 19.46.
Example 5 2-(teit-butvldimethylsiloxy)bisbenz[e,g]iindene
To a suspension of bisbenz[e,g]-2-indanone (35.90 g, 154,5 mmol) and tert-butyldimethykhlorosilane (28,00 g, 185.5 mmol) in benzene (300 mL) was added dropwise DBU (30.60 g, 201.0 mmol) while keeping the reaction mixture cold with an icebath. Stirring was continued for 1 hour at room temperature. The organic phase was washed with water (200 mL), 5% HCl (2 x 200 mL), water (200 mJL) and dried over sodium sulfate. Evaporation of the solvents left a residue which was washed with MeOH (3 x 200 mL) to give the title compoutid (38.35 g, 110.7 mmol, 71.6%) as a slightly pink powder. EIMS (calcd/foimd): 346.1753/346.1744. 3H NMR (CDCI3, d): 8.72-8,67 (m, IH); 8.66-8.62 (m,lH); 8.02-7.96 (m. IH); 7.82-7.99 (m,lH); 7.62-7.57 (ra, 2H): 7.56-7.50 (m, IH); 7.49-7.44 (m, IH); 6.32 (m, IH); 3.73 (m, 2H); 1.03 (s, 9H); 0,33 (s, 6H). l3C NMR (CDCI3, d): 162.16, 139.79; 130.11; 129.41; 128.34; 127.73; 127.21; 126.67; 126.07; 125.53; 124,42; 123.91; 123.38; 123.24; 122.96; 104.55; 39.81; 25.68; 18.29;-4,50.
Example 6 2-(tert-butyldimetfavlsiloxv")-4-7-dimethvlindene
To a solution of tert-butyldimethylchlorosilane (2.85 g, 18,9 mmol) and 4,7-dimethyl-2-indanone (2.53 g, 15.8 mmol, obtained by oxidation of 4,7-3methylindene) in benzene (30 ml) was added DBU (3.13 g, 20.5 mmol) and the

reaction mixture was stirred for 2 hours at room temperatuie. The mixture was diluted with Et20 (50 ml), washed with water (2 x 50 ml), 5% HCl (50 ml) water (2 X 50 ml) and dried over sodium sulphate. Evaporation of the solvents left a dark oU that was dissolved in pentane (30 ml). The unreacted starting materials were Ctystallized at -15 3C and removed by filtration. Evaporation of the solvent gave 3.03 g (69.9%) of fairly pure title compound as an orange oil. 3H NMR (CDCI3, 5): 6.94 (dq. 3J =7.7 Hz, "*J=0.3 Hz, IH),; 6.7S (dq, 3J=7.7 Hz, "*J=0.3 Hz, IH); 5.84 (t, "*J=1 1 Hz. IH); 3.20 (m, 2H); 2.30 (s, 3H); 2.25 (s, 3H); 1.00 (s, 9H); 0.27 (s. 6H);3C N3fR (CDCI3. 6): 162,08; 143.39; 134.89; 129.45; 127.78; 125.49, 123.84: 105.28; 38.80; 25.65; 18.29; lS.21;-4.57.
Example 7
Bisf 2-ftert-butvldimethvlsiIoxv V1 -indenvlkthane
To a solution of 2-(tert-butyldimetiiiylsiloxy)indene (36.96 g, 150.0 mmol) b THF (150 mL) at 0 "C was added dropwise n-BuLi (60,0 mL of a 2.5 M solution in hexanes, 150.0 mmol) and die reaction mixture was stirred overnight at room temperature. The resulting solution was then cooled to -80 "C and treated dropwise with a solution of dibromoethane (14.09 g, 75.0 mmol) in THF (50 mL). After completed addition the reaction mixture was stined overnight at room temperatuie and washed with saturated ammonium cliloride solution (300 mL). Solvents from the organic phase were evaporated and the product was dissolved in Et20 (300 mL); washed with water (2 "3 200 mL) and dried over sodium sulphate. Repeated crystallizations at -15 °C afforded 22.54 g (57.9%) of the title compound as an off-white soHd. The first crystalline fraction consisted of diastereomerically pure material (Mp 108-110 °C). EMS (caicd/foimd): 518.3036/518.3028. 3H NMR (CDCI2, d, major diastereomer); 7.18-7.07 (m, 6H); 6.97 (td» 3; =: 7.4 Hz, 3} = 1.3 Hz, 2H); 5.66 (s, 2H); 3.17 (m, 2H); 1.89-1.84 (m, AA", 2H); 1.59-1.54 (m, BB", 2H); 0.94 (s, 18H); 0.23 (s, 6H); 0.21 (s, 6H). l3c NMR (CDCI3, d, major diastereoraer): 164.96; 144.39; 140.62; 126.50; 122.58; 122.41; 118.74; 104.97; 49.18: 25.67; 24.34; 18.12; -4.68; -4.88. 3H NMR (CDCI3, d, minor diastereomer): 7.17-7.05 (m, 6H); 6.97 (td, 3J =7.4 Hz, 4j = 1.2 Hz, 2H); 5.63 ($, 2H); 3.21 (m, 2H); 1.76-1.75 (m, 4H); 0.94 (s, 18H); 0.22 (s, 6H); 0.20 (s, 6H). l3c NMR (CDCIs/d, minor diastereomer): 165.18; 144.35; 140.68; 126.53; 122.71, 122.35; 118.74; 104.87; 49.04, 25.67; 25.30; 18.14, -4.77.

Example 8 Bisa-ft-faexvldimethvIsiloyvjindeivvUethane
To a solution of 2-(t-hexyldimethylsiloxy)indene (68.62 g, 250.0 mmoi) in THF (250 mL) at 0 "C was addsd dropwise n-BuLi (100.0 mL of a 2.5 M solution in hexanes, 250.0 nunol), and the reaction mixture was stirred overnight at room temperature. The resulting solution was then cooled to -80 "C and treated dropwise with a solution of dibromoethane (23.48 g, 125.0 nunol) in THF (100 mL). After completed addition the reaction mixtiure was stirred overnight at room tempeiatute and washed with saturated ammonium chloride solution (350 mL). Solvents from the organic phase were evaporated, and the product was dissolved in Et20 (350 mL), washed with water (2 x 300 mL) and dried over sodiimi sulphate. Repeated ciystallizations at -15 "C afforded 37.48 g (52.2%) of the title compound as off-white crystals. The first crystalline fraction consisted of diastereomerically pure material that was used for spectral characterization, EIMS (calcd/found); m/e 574.3662/574,3659. 3H NMR {CDCl-3, d): 7.22 - 7.07 (m, 6H); 6.97 (td, 3j = 7.4 Hz, 4j « 1.2 Hz, 2H); 5.65 (s, 2H); 3.15 (m, 2H); 1.91 - 1.84 (m, AA", 2H); 1.67 (sept, h = 6.8 Hz, 2H); 1.57 - 1.50 (m, BB", 2H); 0.89 (m, 24H>; 0.27 (s, 6H); 0.24 (s, 6H). 13c NMR (CDCI3, d): 164.75; 144.45; 140.58; 126.46; 122.60; 122.33; 1IS.68; 104.96; 49.24; 33.93; 25.03; 24.32; 20.14; 20.02. 18.51; 18.47; -2.66; -2.95.
Example 9
Bisr2-f cyclohexvtdimethvlsiloxv)-1 -indenvDethane
To an ice-cooled solution of 2-(cyclohexyldimethylsiIoxy)indefle (13.62 g, 50.0 mmol) in THF (50 mL) was added dropwise n-BiiLi (20.0 mi of a 2.5 M solution in hexanes, 50.0 mmol) and the reaction mixture was stirred ovemiglit at room temperature. The resulting solution was then cooled to -80 °C and treated diopwise with a solution of dibromoethane (4.70 g, 25.0 mmol) in THF (30 mL). The reaction mixture was gradually warmed to room temperature, stirred overnight and washed with saturated airunonium chloride solution (150 mL). The organic phase was diied over sodium sulfate. Solvents were evaporated and the remaining oil was dissolved in £t20 (100 mL). Repeated crystaUizations gave a total yield 4.03 g (28.2%) of tl\e title compound as off-white crystals. The first crystalline fraction was used for spectral characterization. EIMS (calcd/found): m/e 570.3349/570.3342. 3H NMR (CDCI3, d): 7.19 - 7.07 (m, 6H); 6.99 (td, 3j = 7.3 Hz, 3J = I.3 Hz, 2H); 5.65 (s, 2H); 3.17 (m, 2H); 1.84 - 1.79 (m, AA", 2H); 1.73 (m, lOH); 1.59 - 1.54 (ra, BB",

r
2H); 1.20 (m, lOH): 0.84 (m, 2H); 0.22 (s, 6H); 0.22 (s, 6H). I3c NMR (CDCI3, d): 164.98; 144.47; 140.65; 126.51; 122.52; 122.33; U8.72; 104.64; 49 09- 27 72-26.80; 26.48; 26.37; 24.29; -3.60,
Example 10 Bisf2-fteit-butvldiphenvlsiloxv1iiidenvllethane
To a solution of 2-(tert-butyldiphenylsiloxy)iiidene (32.6 g, 88.0 iranol) in i"HF (200 inL) at 0 "C was added dropwise n-BuLi (35.5 mL of a 2.5 M solution in hexane, 88.8 lumol), and the reaction mixture was stured overnight at room temperature. The resulting solution was tlien cooled to -80 "C and treated dropwise with a solution of dibromoethane (8.26 g, 44.0 mmol) in THF (50 mt). The reaction mixture was gradually wanned to room temperature, stiired overnight and washed with satiu"ated ammoniura chloride solution (2 x 300 mL). The organic phase was dried over sodium sulfate. Evaporation of the solvents left a brow3 oil that was dissolved \x\ boiling Et20 (300 mL). Cooling to -15 "C gave 13.7 g (40.7%) of the title compound as a diastereomerically pure white microctystalline powder. EIMS (calcd/found): m/e 766.3662/766.3641. 1H NMR {CDCI3, d): 7.78 - 7.75 (m, 4H); 7.71 - 7.68 (m, 4H); 7.48 - 7.33 (m, 12H); 7.22 - 7.20 (m, 2H); 7.09 - 7.05 (m, 2H); 6.93 - 6.88 (m, 4H); 5.28 (s, 2H); 3.36 (m, 2H); 2.21 - 2.15 (m, AA", 2H); 1.85 -1.79 (m, BB", 2H); 1.06 (s, 18H), l3c NMR (€0013, d): 164.06; 144.19; 140.54; 135.45; 132.28; 131.91; 130.06; 129.99; 127.84; 127.79; 126.45; 122.65; 122,54; 119.06; 106.81; 49.25; 26.61; 25.10; 19.38. The mother liquor was evaporated to dryness and dissolved in boiling pentane (150 mL). Concentration and cooling to -15 °C gave the second crop 1.62 g (4.8%) of the title compound as a brown powder enriched in 3e minor diastereomer (total yield 45.5%).
Example U Bis(2-ftert-butvldimethvlsiloxv3bisben2fe.g]indenvne thane
To an ice-cooled solution of 2-(tert-butyldimethyIsiloxy)bisbenz[e,g]indene (20.00 %, 63,48 mmol) in THF (SO mL) was added dropwise n-BuLi (25.4 mL of a 2.5 M solution in hexanes, 63.50 mmol) and the reaction mixture stirred at room temperature for 1 hour The solvents were removed in vacuo and toluene (200 mL) was added. The resuUi:ig solution was cooled to -80 °C and dibromoethane (5.95 g, 31.67 mmol) in toluene (20 mL) was added dropwise. The reaction mixture was gradually waraied to room temperature, stirred overnight and washed with saturated ammonium chloride solution (2 x 100 mL). The organic phase was dried over

sumiuii suiiatc. i3onceniration ana cooiuig to -m "L gave the title compound (900 mg, 1.25 mmol, 3.9%) as an off-white solid. EIMS (calcd/found); ra/e 718.3662/718.3659. 3H NMR (CDCh, d): 8.73-8.69 (m, 2H); 8.66 (dt, 3j = 8 2 Hz, 4j = 0.6 Hz. 2H); 8.02-7.98 (m. 2H); 7.63-7.58 (m, 6H); 7.42 (ddd, 3j = 8.2 Hz, 3j - 6.9 Hz, 4j = 1.3 Hz, 2H); 7.34 (ddd. 3j = 8.2 Hz, 3j 3 6.9 Hz, 4/ = 1.2 Hz, 2H); 6.17 (d, 4j = 0.4 Hz, 2H); 3.57-3.54 (m, 2H); 2.09-2.06 (m, 2H); J.76-1.73 (m, 2H); 0.72 (s, 18 H); O.ll (s, 6H); 0.03 (s, 6H). 13C NMR (CDC1s, d): 166.68; 139.37; 131.67; 130.32; 129.25; 127.93; 127.04; 126.70; 125.91; 125.46; 124.34; 123.61; 123.43; 123.20; 122.97; 102.67; 49,93; 25.48; 23.68; 18.04;-4.82;-5.03.
Example 12 Bisri-("triinethvlsilviV2-("tert-butvldimethvlsiloxvV3-indenvnetliane
To a solution of fais(2-(tert-butyldimethylsiloxy)-l-indenyl)ethane (10.38 g, 20.0 mmol) in THF (100 mL) at -20 °C was added dropwise n-BuLi (16.1 mL of a 2.5 M solution in hexane, 40.2 mmol) and the reaction mixture was stirred for 3 hours at room temperature. To the resulting solution was added dropwise chlorotrimethysilane (6.S5 g, 63.0 mmol 8.0 mL) at 0C. After completed addition the reaction mixture was stirred overnight at room temperature and the solvents were evaporated. The remaining orange solid was extracted with CH2CI2 and filtrated through celite. The solvent was evaporated and the product was dissolved in Et20 (150 mL). Concentration and cooling to 0 "C gave 10.29 g (77.6%) of a 2:1 diastereomeric mixture of the title compound as off-white crystals. EIMS (calcd/foimd): m/e 662,3827/662.3834. 3H NMR (CD2CI2, d, major/minor diastereomer): 7.51-7.49 (m, 2H, major); 7.42-7.40 (m. 2H, minor); 7.29-7.24 (m= 4+2H, major/minor): 7.22-7,17 (m. 2H, minor); 7.08-7.02 (m, 2+2H, major/minor); 3.29 (s, IH, minor); 3.27 (s, IH, major); 3.00-2.96 (m, AA", 2H, minor); 2.72-2.65 (m, AA"BB". 4H, major); 2,44-2.40 (m, BB", 2H, minor): 1.02 (s, ISH, major); 1.01 (s, 18H, minor); 0.20 (s, 6H, minor); 0.19 (s, 6H. major); 0.10 (s, 6H, minor); 0.05 (s. 6H, major); 0.02 (s, iSH, minor); 0.01 (s, ISH, major). l3C NMR (CD2CI2, d, major diastereomer); 158.32; 144.56; 139.24; 125.09; 122.74; 121.98; 119.89; 118.08; 45.08; 26.14; 24.06; 18.52; -2.39; -3.40; -4.66. 33c NMR (CDCI3, d, minof diastereomer): 158.08; 144.50; 139.14; 124.97; 122.62; 121.95; 119.95; 118.50; 45.13; 26.14; 23.86; IS.47; -2.29; -3.40; -4.24.

Exapiple 13 DimethvIbisf2-(tert-butvldiinethvIsiloxvlindenvl)silaae
To a solution of 2-(tert-butyldimethylsiloxy)indene (12.32 g, 50.0 mmol) in Et20 (50 mL) at 0 X was added dropwise n-BuLi (20.0 ml of a 2.5 M solution in hexane, 50.0 mmol) and the reaction mixture was stiired overnight at room temperature. The resulting solution was then added dropwise to a solution of dimethyJdichlorosilane (3.03 ml, 25.0 mmol) in Et20 (25 mL) at 0 "C The reaction mixture was stirred overnight at room temperature and washed with saturated ammonium chloride solution (150 mL), water (3 x lOO mL) and dried over sodium sulfate. Evaporation of the solvents left a red oil that was dissolved in a LI mixture of MeOH and acetone. Concentration and cooling to -30C gave 5.78 g (42.1%) of the title compound as slightly yellow crystals. The first crop consisted exclusively of the racemic diastereomer. EIMS (calcd/found): m/e 54S.2962/548.2958. Mp: 92-94 °C. iH NMR (CDCls, d); 7.22-7.14 (m. 6H); 6,98 (td, 3j =* 7.3 Hz, 4j = 1.4 Hz, 2H); 5 85 (s, 2H); 3.99 (s, 2H); 0.97 (s, 18H); 0.34 (s, 6H); 0.28 (s, 6H); -0.23 (s, 6H). 13c NMR (CDCI3, d): 164.96; 144.44; 137.55; 125.13; 122.75; 121.41; 118.83; 104.00; 43.06; 25.77; 18.20; -4.34; -4.88; -6.99. The oily residue was washed with copiously with cold MeOH (3 « 50 mL), cold pentane (50 mL) and dried in vacuo to yield 3.47 g (24.8%) of the fairly pure meso diastereomer as a red oil (total yield 66.9%).
Examptg 14 Dimethvlbisf2-ft-hex\3ldimethvlsilo>cv)indenvllsilane
To a solution of 2-(t-hexyldimethyUiIoxy)indene (35.58 g, 129.6 mmol) in £t20 (120 mL) at 0 "C was added dropwise n-BuLi (52.4 ml of a 2.5 M solution in hexane, 130.9 nnnol) and the reaction mixture was stin-ed ovenught at room temperature. The resulting solution was then added dropwise to a solution of dimethyldichlorosilane (7.9 mL, 64.8 mmol) in Et20 (50 mL) at 0 "C. The reaction mixture was stirred ovemiglrt at room temperature and washed with saturated ammonium chloride solution (300 mt), water (2 x 200 mL) and dried over sodium sulfate. Evaporation of the solvents left a red oil that was dissolved in a 4; 1 mixture of MeOH and acetone. Concentration and cooling to -30 "C gave 11.67 g (29.7%) of the titie compound as a white powder. The ctystalline fu"st crop consisted exclusively of the racemic diastereomer. EIMS (calcd/found); m/e 604.3588/604.3585. iR NMR (CDCI3, d): 7.22 - 7.13 (m, 6H); 6.98 (td, 3j = 7.3 Hz, "3J - 1.4 Hz, 2H); 5.85 (s, 2H); 3.99 (5, 2H); 1.72 (sept. 3j - 6,9 Hz, 2H); 0.94

(s, 6H); 0.94 (s, 6H); 0.90 (d, 3j = 6,9 Hz. 6H); 0.89 (d, 3j = 6.9 Hz, 6H); 0.38 (s, 6H): 0.34 (s, 6H); -0.23 (s, 6H). l3c NMR (CDCI3, Example 15 fBisf2-("tert-butvldimethvlsiloxv)bisbenz[e.g1indenvi")l2ircoiiiumdichloride
To a solution of 2-(tert-butyldimethyisiloxy)bisbenz[e,gJindetiene (6.83 g, 19.7 mmol) in THF (50 niL) was added dropwise n-BuLi (7.9 mL of a 2.5 M solution in hexanes, 19.7 itiinol) at -20 "C. The resulting red solution was allowed to warm to room temperature and added via cannula to a solution of ZrCl4 (2,24 g, 9.6 mmol) in THF (50 mL). The reaction raixture was refluxed for 20 h. Evaporation of the THF left a solid that was extracted with CH2CI2 (50 mL) and filtrated througli celite to remove lithium chloride. Evaporation of the CH2CI2 left a red oily solid which was washed with Et20 (2 x 50 mL) to leave 2.97 g (34.0%) of the title compound as a pale green powder. Single crystals for X-ray diffraction were obtained from a concenteated toluene solution at -15 "C- In the EIMS mass spectrum of the title compound parent ions of composition C46H5oSi202ZrCl2""were observed m tlie appropriate isotope ratios at m/e = 850-859. 3H NMR (CDCI3, d): 8.45 (ra, 4H); 7.66 (m, 4H); 7.50-7.41 (m, 8H); 6.24 (s, 4H); 1.08 (s, ISH); 0.34 (sa2H). 13c NMR (CDCI3, d): 153.11; 129.88; 129-02; 128.21; 128.13; 126.95,; 126.82; 124.25; 123.37; 118.32; 97.22; 25.80; 18.48; -4.12.
Example 16 rac-ethvlenebisf2-tert-butvldimethvlsiloxvindenvl)zirconiumdichloride
To an ice-cooled solution of bis(2-(teTt-butyldimethyUiioxy)indenyl)ethane (5.37 g, 10.3 mmol) in THF (50 mL) was added dropwise n-BuLi {8.3 mL of a 2.5 M solution in hexanes, 20.7 mmol) and the reaction mixture was stirred overnight at room temperature. The resuhant off-yellow suspension was then added via cannula to a suspension of ZrCU (2.41 g, 10.3 mmol) in THF (20 mL) at -SO "C. The reaction mixture was gradually warmed to room temperature and stiired overnight. Evaporation of tlie solvents left a yellow solid that was exh-acted with CH2C12 (150 mL) and filtrated through celite to remove litluum chloride. Concentration and cooling to -30•€ gave 1.47 g (21.0 %) of the titie compound as a yellow

tnicrociystalline solid. In the EIMS mass spectrum of the title compound parent ions of composition C32H44Si202ZrCl2"3 were observed in the appropriate isotope ratios at m/e - 676-6S4. 1H NMR (CDzCh): d 7.64 (dq, J = 8.6 Hz, 1.9 Hz, 0.9 Hz, 2H); 7.31-7.27 (m, 4H); 7.07-7.03 (m, 2H); 5.93 (d, J = 0.8 Hz. 2H); 4.01-3.90 (m, AA", 2H); 3.58-3.47 (m, BB", 2H); i.OO (s, 18H); 0.20 (s, 6H); 0.19 (s, 6H). L3c NMR (CD2CI2); d 150.12; 126.17; 125.14; 124.86; 124.79; 123.35; 116 99-108.54; 98.61; 26.30; 25.80; 18.61; -3.94; -4.27.
Example !7
rac-rethvlenebisf"2-("tert-butvldi]netIiylsiioxvV4.5.6.7-tetrahvdroiTidenvli]2ircQnium dichloride
A mixture of rac-[ethylenebis((2-tert-butyldimethylsiloxy)indenyl)lzirconiuin dichloride (1.00 g, 1.47 ramol) and Pt02 (20 mg) in CH2CI2 (150 mL) was hydrogenated at 70 bar in a stirred reactor for 16 h. The light green suspension was filtered through Cclite and the solvent evaporated. The residue was dissolved in hexanc (50 mt) and cooled to 0 "C to provide O.SO g (79.2""/o) of the title compound as a light green microcrystalline solid. In the EIMS mass spectrum of the title compound parent ions of composition C32H52Si2022rCl2"3 were observed at m/e « 684-692 in the appropriate isotope ratios. 3H NMR (CD2CI2, d): 5.69 (s, 2H); 3.39-3.29 (m, AA; 2H); 3,04-2.97 (m, 2H); 2.85-2.77 (ttu 2H): 2.73-2.64 (m, BB", 2H); 2.48-2.34 (m, 4H); i.90-1.70 (m, 4H); 1.59-1.42 (m, 4H); 0.92 (s, 18H); 0.20 (s, 6H);0.16(s, 6H). 13c NMR (00202, d): 142.24; 127.66; 117.29; 114,18; 106.45; 25.46; 24.46; 23.80; 22.05; 21.92; 21.75; 18.10; -4.09; -4.65.
Example 18
rac-ethvlenehisC2-tert-butvldimethvlsiloxv- l-inHfinyl)hafaittm dichloride
To a solution of bis(2-(tert-butyldimethylsiloxy)tQdenyl)ethane (10.38 g, 20,0 ramol) ill THF (80 mL) at 0 "C was added dropwise n-BuLi (16.1 mL of a 2.5 M solution in hexane, 40.2 mmol) and the reaction mixture was stirred overnight at room temperature. The solvents were removed in vacuo and the resulting off-white powder was mixed with HfC3 (6.41 g, 20.0 mmol). The mixture was cooled to -SO "C and precooled CH2CI2 (150 ml) was added, Th« light yellov? suspension was gradually wanned to room, temperature, stiiTed overnight and filtrated through celite to remove lithium chloride. Concentration and cooling to -30 °C gave 1.96 g (12.8%) of the title compound as a light yellow microcrystalline solid. In the EIMS mass spectrum of the title compound, parent ions of composition

C32H44Si202HfCl2"*were observca m me appropriate isotope ratios at m/e = 760-774. iH NMR (CD2CI2. d): 7.64 (dq, J - 8.5 Hz, 1.8 Hz. 1.0 Hz, 2H)- 7 34 - 7 25 (m, 4H); 7.05 - 7.01 (in, 2H); 5.86 (d. 4j = o.7 Hz, 2H); 4.02 - 3.92 (AA2H)-3 3.71- 3.61 (BB; 2H); 1.02 (s, 18H): 0.22 (s, 6H); 0.21 (s, 6H). 13c NMR (CD2CI2, d): 148,64; 126.19; 124.97; 124.35, 124.30; 123.49; U5.47; 105 37-96.46, 25.84; 25.52; 18.62; -3.92; -4.26,
Example 19 rac-rethvlenebisf2-(t-hexvldijnethv]siloxv){ndenvl")1zirCQrutimdicliIoride
To an ice-cooled solution of Ms(2-(t-hexyMimetliylsiloxy)indenyl)ethane (11-50 g, 20.0 imnol) in THF (100 mL) was added dropwise n-BuLi (16.0 mL of a 2.5 M solution in hexane, 40.0 irunol) and the reaction mixture was stiired overnight at room temperature. The resultant off-yellow suspension was then added via cannula to a suspension of ZrCU (4.66 g, 20.0 irnnol) in THF (25 mL) at -80 "C. Tiie reaction mixture was gradually wanned to room temperature and stirred overnight. Evaporationoftliesolventsleftayellowsolid that was extracted with CH2CI2 (150 mL) and filtrated through C6lite to remove lithium chloride. Concentration and cooling to -30 "C gave 3.25 g (22.1 %) of the title compound as a yellow raicrociystalline solid. Single crystals for X-ray dif&action were obtained from a saturated toluene solution at ambient temperature. In the EIMS mass spectrum of the title compoimd parent ions of composition C35H52Si202ZrCl2"*were observed in the appropriate isotope ratios at m,"e = 732-740, 3H NMR (CDoCl3, d): 7.66 (dq, J = 8.6 Hz, 1.8 Hz, 1.0 Hz, 2H); 7.35 - 7,29 (m. 4H); 7,08 - 7.04 (m, 2H), 5.95 (d, 4j = 0.6 Hz, 2H); 4.04 - 3.94 (m, AA". 2H); 3.56 - 3.46 (m, BB", 2H); 1-74 (sept. 3j = 6.8 Hz, 2H); 0.99 (s, 6H); 0.97 (s, 6H); 0.95 (d, 3j - 6.8 Hz, 6H); 0.94 (d, 3j :. 6.8 Hz, 6H); 0.26 (s, 6H); 0.25 (s. 6H). 33c NNIR (00202, d): 150.48; 126.13; 125.18; 125.10; 124.85; 123.32; 116.94; 98.53; 34.22; 26,41; 25.84; 20.35; 20.14; 18.80; 18.64;-1.62;-2.01
Example 20
rac- and masn-(limethvlsilvlenebisf2-tert-butvldimethylsiloxvindenvl")zirconxum
iichlorides
To a solution of dimethylbis(2-(tert-butyIdimethyIsiloxy)indenyl)silane (10.98 g, >0,0 mmol) in Et20 (40 mL) at 0 ""C was added dropwise n-BuLi (16.0 mL of a 2.5 vl solution in hexane, 40.0 mmol) and the reaction mixture was stirred oveinight at 00m temperature. The solvents were removed in vacuo to leave an off-white

powder that was mixed with ZrCU (4.66 g, 20 mraol). The mixture was cooled to -80 °C and preceded CH2CI2 (150 ml) was added. The liglit yellow suspension was gradually wanned to room temperature, stirred overnight and filtrated through celite 3 to remove lithium chloride. Concentration and cooling to -30C gave 7.95 g (56.0%) of an approximately 2:1 rac/meso mixture of the fairly pure title compound as a bright yellow powder. In the ElMS mass spectrum of the title compound, parent ions of composition C32H46Si302ZrCl2"*were observed in tiie appropriate isotope ratios at m/e 706-714. Small amounts of the fairly pure rac diastereomer of the tide compound were obtained by carrying out the reaction in THF solution, foUowed by removal of LiCl and ciystallization from Et20.H HMR (CD2CI2, d, rac): 7.47-7.44 (m, 2H); 1.7>1"1.H (m, 4H); 6.91-6.87 (m, 2H); 6.22 (d, "3J = 0.8 Hz, 2H); 1.19 (s,6H); 0.92 (s, 18H); 0.27 (s, en); 0.21 (s, 6H). l3c NMR (CDsC1a, d, rac); 155.89; 128.69; 127.13; 126.84; 125.07; 124.94; U9.69; 104.50; 73.22; 26.12; 19.23. 1.04;-3,36;-3.S7.
POLYMERIZATION TESTS Example 21
The polymerizations were perfonned in a 0.5 1 Biichi glass autoclave m 200 ml of toluene. In a typical run half of the MAO/toluene solution was added to the reactor and stirred for 5 minutes in order to reduce any impurities in the reactor. In a parallel procedure 10-15 pmmol of the metallocene was dissolved in the remaining half of the MAO/toluene solution and preactivated at 25C for 5 min. The catalyst/activatoE mixture was charged into tlie reactor and the polymerization was started by introducing tiie olefin monomer. The polymerization was interrupted after 20 or 60 minutes by addition of ethanol or methanol. The polymer was analyzed after being washed with etbanoI/HCl or methanol/HCl.
Vlethylaluminoxane (R-VO) was used as 29.3 w-% toluene solution (Al total 13.1 % "/o w/w, Ai as TMA 3.50 % w/w). High purity ethylene and propylene (99,5 %) vere used as monomers.
:he results are presented in tlie Table 1 below.

Example 33
The polyraerization with the fmetalioceneJ3[B(C6F6)4r catalyst system were cairied out at -20C and 2.0 bai propylene pressure using triethylalumina (TEA) as impttrity scavenger. In a typical run 0.3 g of TEA was stirred with 50 ml of toluene followed by the addition of 5 umol of the metallocene. The cation forming agent (14 Minol) was added via a syringe. The polyraerization was interrupted after 60 min by addition of ethanol or methanol. The polymer was analyzed after being washed with ethanol/HCl or methanoI/HCl.

WE CLAIM:
1. A method of preparing catalyst components for olefin polymerization and copolymerization wherein 2-indanone is reacted in a solvent which is dimethylformamide or tetrahydrofurane with a base which is imidazole, trithylamine or 1, 8-diazobicyclo [5.4,0] undec-7 - ene and a chlorosilane to form 2-siloxyjndene according to the following reaction scheme:

2. The method according to claim 1, wherein the base is selected from
imidazole and triethylamine (TEA) and chlorosilanes are selected from tert-
butyldimethylchlorosilane, t-hexyldimethylchlorosilane and
cyclohexyldimethyl- chlorosilane.
3. The method according to claims 1 or 2, wherein the reaction is
continued according to the following reaction scheme:

4. The method according to claims 1 or 2, wherein the reaction is continued
according to the following reaction scheme (X):

5. The method according to claims 1 or 2, wherein the reaction is continued according to the following reaction scheme:

6. A process for polymerizing olefins wherein one or more olefin selected fi*om ethylene, propylene, hutylene, pentene, hexane, heptene and octene is/are contacted under polymerization conditions in the presence of the catalyst prepared by the process as claimed in any one of the preceding claims, the said catalyst comprising a catalyst precursor having the formula

wherein: each IndY is the same or different and is one of a mono- or polysubstituted, fused or non-fused, homo- or heterocyclic indenyl ligand, dihydroindenyl ligand or tetrahydroindenyl ligand, which ligand is

substituted at the 2-position of its indenyl structure by the group Y, which group Y has the following structure (II):

wherein D is one of silicon or gennanium, R3 R3 and R4 are the same or different and are one of a hydrogen atom, a C1-C10 hydrocarbyl group or a C1-C10 hydro- carbyloxy group, or at least two of R3 R3 and R4 form together a C2-C20 ring structure; M is a transition metal of group 4 of the Periodic Table and is bound to the ligand IndY in at least an ri5 bonding mode; each R is the same or different and is one of a hydrogen atom, a halogen atom, a C1-C10 hydrocarbyl group, a C1-C10 hydrocarbyloxy group, a tri-hydrocarbyl silyl group or two R form together a C2-C20 ring structure; B is a bridge atom or group between two IndY ligands or between one IndY ligand and the transition metal M; m is 1 or 2; o is 0 or 1; and n is 4-m when B is a bridge atom or group between two IndY ligands, or n is 4-m-o when B is a bridge atom or group between one IndY ligand and the transition metal M.

7. The process according to claim 6, wherein said catalyst precursor has the formula III;

where M is a metal selected from zirconium, titanium or hafiiium, D is an element selected from silicon (Si) or germanium (Ge), B is a bridge comprising at least one of-(CH 2 )n, ~Si(R. 3)2- or -Ge(R3)2-, wherein n = 1-8 , R1 and R2 are the same or different groups selected from hydrogen, C1-C1o alkyl group, C1-C10 alkoxy group, C6-C10 aryl group, C6-C10 aryloxy group, C2-C,oalkenyl group, C2-C10 aryl alkyl group, C2-C10 alkyl aryl group, Cg-C40 arylalkenyl group or a halogen atom,
R3, R3-R6 are the same or different group selected from hydrogen, C1-C1o alkyl group, C1-C10 alkoxy group, C6-C10 aryl group, Cg-C10 aryloxy group, C2-C10 alkenyl group, C7-C22 arylalkyl group, C7-C22 alkyl aryl group, and

C8-C40 arylarkenyl group. R3 and R3 -groups can also be connected to each other to form a ring structure and R4 may also be a ring structure.
8. The process according to claim 6 or 7, wherein M is zirconium and D is silicon.
9. The process according to claim 7, wherein R1 and R2 are preferably the same and most preferably they are halogen atoms, preferably chlorine atoms.
10. The process according to any one of claims 7 to 9, wherein R3 and/or R3 is C1-C10 alkyl or aryl group and most preferably methyl group and R 4 is C1-C10 alkyl or aryl group, preferably tert-butyl group, t-hexyl group or cyclohexyl group.
11. The process according to any one of claims 7 to 10, wherein D is Si, B is -CH 2CH 2-, R=R=R2 and is chlorine, R3 is CH3 and R5-R6 is aromatic or fused aromatic or alkyl or hydrogen.
12. The process according to any one of claims 7 to 11, wherein said catalyst precursor is based on a 2 tri-hydrocarbyl siloxy indene, 2-tri-hydrocarbyloxy siloxy indene, 2-tri- hydrocarbyloxy germyloxy indene or 2-tri-hydrocarbyloxy germyloxy indene compound having the general formula:

wherein D is one of silicon and germanium; R3 R3 and R4 are the same or different and are one of a hydrogen atom, a C1-C10 hydrocarbyl group or a C1-C1o hydrocarbyloxy group, or at least two of R3 R3 and R4 form together a C2-C20 ring structure; R3 is a four-atom chain forming an unsubstituted or substituted, further non-fused or further fused, homocyclic (=isocyclic) or heterocyclic, unsaturated or saturated, aliphatic or aromatic six-membered ring M and R3, R and R10 are the same or different and are one of a hydrogen atom, a C1-C10 hydrocarbyl group, a C1-C10 hydrocarbyloxy group, a tri-C1-C10 hydrocarbyl silyl group or a tri- C1-C\o hydrocarbyloxy silyl group, or one of R3 and R3 may be a bridge atom or group B to a cyclopentadienyl; fluorenyl or indenyl group.
13. The process according to claim 12, wherein 2-tri-hydrocarbylsiloxy indene or 2- tri-hydrocarbylgermyloxy indene has the following formula:

wherein: R3, R 3 -R3 ars the same or dififerent and are one of a hydrogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C10aryl group, a C1-C10 alkenyl group, a C7-C22 aiylalkyl group, a C7-C22 alkylaryl group, or a Cg-C23 arylalkenyl group, or at least two of R\ R3 and R"* form together a C2-C10 ring structure, and R 3 R 3 and R3** are the same as above.
14. The process according to claims 12 or 13 wherein 2-tri-hydrocarbylsiloxy indene or 2-tri-hydrocarbylgermyloxy indene has the general formula (VI)

wherein: R3 R3, R4 - R3 R3 R° and D are the same as above; and B is a bridge of at least one of the groups -{CH2)n-, -SiR \- or -GeR 32-, wherein n is 1-8 and R3 is the same as above.

10. the processaccording to any one of claims 12 to 9, wherein 2-tri-hydrocarbylsiloxy indene or 2-tri-hydrDcarbylgermyloxy indene D is silicon.
16. A method of preparing catalyst components for olefin polymerization substantially as herein described and exemplified.
17. A process for polymerizing olefins in the presence of a catalyst substantially as herein described and exemplified.

Documents:

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189-mas-1997 abstract.pdf

189-mas-1997 claims duplicate.pdf

189-mas-1997 claims.pdf

189-mas-1997 correspondence others.pdf

189-mas-1997 correspondence po.pdf

189-mas-1997 description (complete) duplicate.pdf

189-mas-1997 description (complete).pdf

189-mas-1997 form-2.pdf

189-mas-1997 form-26.pdf

189-mas-1997 form-4.pdf

189-mas-1997 form-6.pdf

189-mas-1997 petition.pdf

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Patent Number

198421

Indian Patent Application Number

189/MAS/1997

PG Journal Number

08/2007

Publication Date

23-Feb-2007

Grant Date

20-Jan-2006

Date of Filing

30-Jan-1997

Name of Patentee

M/S. BOREALIS A/S

Applicant Address

LYNGBY HOVEDGADE 96, DK-2800 LYNGBY

Inventors:

#	Inventor's Name	Inventor's Address
1	LEINO	REKO, KERTTULINKATU, 14 A 9, FIN-20500 TURKU.
2	LUTTIGHEDDE	HENDRIK, TOPOISTENTIE 43, FIN-21270 NOUSIAINEN.
3	NASMAN	JAN, RAKUUNATIE 58 A C48, FIN-20720, TURKU.
4	WILEN	CARL-ERIK, VASTERLANGGATAN 29 A 3, FIN-20100 TURKU.

PCT International Classification Number

C08 F 4/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	960437	1996-01-30	Finland