A new synthetic route to C-2 bridged indenyl metallocenes utilizing the anion of 1-indanone has been developed. Two new ansa-zirconocene complexes, isopropylidene(cyclopentadienyl)(2-indenyl)ZfCl2 ( 1a) and isopropylidene (cyclopentadienyl)(2-(1-methyl-indenyl))ZrCl 2 (1b) were synthesized and examined as precursors for the polymerization of α-olefins. These metallocenes were shown to be active for the polymerization of ethylene and for the oligiomerization of propylene when activated with excess methylaluminoxane (MAO). A new route to isopropylidene bridged 2-indenyl metallocenes has been developed. Two new C-2 bridged ansa-zirconocenes, isopropylidene(1-indenyl)(2-indenyl)ZrCl 2 (10) and isopropylidene-bis(2-indenyl)ZrCl2 (11) have been synthesized and examined as pre-catalysts for the polymerization of ethylene and propylene. Both metallocenes were highly active for the polymerization of ethylene and the oligiomerzation of propylene when activated with excess methylaluminoxane (MAO) or [CPh3]+[B(C6F 5)4]−/Al(CH2CH(CH3) 2)3. The new pre-catalysts 10 and 11 were examined for the copolymerization of ethylene and styrene when activated with excess MAO. Both complexes 10 and 11 were highly productive for the copolymerization of ethylene and styrene with styrene incorporations of 29.2% and 21.0% by weight, respectively. 13C NMR studies indicated that there were no sequential or alternating styrene insertions in the copolymers, giving a unique polymer microstructure. X-ray diffraction studies indicated that the styrene units were excluded from the polymer lamella and that π-π interactions were taking place between the aromatic rings. The effect ansa-phenyl coordination in indenyl titanium half-sandwich complexes on α-olefin polymerization has been tested using indenyl titanium trichloride (19), 3-benzyl-indenyl titanium trichloride (20), and 3-benzhydryl-indenyl titanium trichloride (21). For styrene polymerization, the presence of pendant phenyl substituents decreases polymerization activity, decreases percent syndiotacticity, increases molecular weight, and decreases the observed melting point of the polymer. For ethylene polymerizations, the presence of pendant phenyl substituents decreases polymerization activity and generally increases molecular weight.

Eight new half-sandwich titanium catalyst precursors were prepared, and their catalysis of syndiospecific styrene polymerization when activated by methylaluminoxane was studied. Phenyl substitution increases polymerization activity in the order 15 $<$ 13 $<$ 11; the opposite trend was observed for the yield of syndiotactic polystyrene (s-PS). Benz (e) IndTiCl$\sb3$ (17) as well as the 2-methyl (19) and 1,2,3-trimethyl (23) derivatives were synthesized. Catalysts 17/MAO and 19/MAO exhibit exceedingly high activity, and produce s-PS with high stereoregularity and molecular weight. A variety of methoxy and phenyl-substituted (indenyl)titanium trichloride complexes were synthesized, and these precursors were used to polymerize styrene, ethylene, and propylene. The complexes, when activated with MAO, show only low activity for the polymerization of styrene and ethylene and no activity for propylene polymerization. Oxygen-aluminum coordination between the methoxy group and MAO could be one of the deactivating interactions. 9- ((2-t-Butylamino)ethyl) fluorene (66) was synthesized by the use of (1-chloro-2-t-butylamino)ethane (65) which provided convenient routes to 66 as well as 3- ((2-t-butylamino)ethyl) indene (67). Deprotonation of 66 with 2 equivalents of butyllithium followed by addition of ZrCl$\sb4$ or HfCl$\sb4$ led to (1-($\eta\sp1$-t-butylamido)-2-($\eta\sp5$-9-fluorenyl)ethane) zirconium (68) and hafnium (69) dichloride, respectively. Complexes 68 and 69 when activated with methylaluminoxane (MAO) are active catalysts for the polymerization of ethylene. A variety of new unbridged metallocene complexes were synthesized. Bis($\eta\sp5$-2-methylbenz (e) indenyl)zirconium dichloride (80) was activated with both MAO and triphenylcarbenium tetrakis(pentafluorophenyl)borate (trityl)/triisobutylaluminum (TIBA) producing polypropylene with varying molecular weight depending on polymerization temperature. The precursor ($\eta\sp5$-4,5,6,7-tetrahydro-1,2-dimethylbenz (e) indenyl)zirconium dichloride (101) when activated with trityl/TIBA produced a mixture of atactic and isotactic polypropylene (i-PP) with 51% mmmm pentads. The silicon bridged ansa-metallocene (dimethylsilanediylbis($\eta\sp5$-1,1$\sp \prime$-(4,5,6,7-tetrahydro-2-methylbenz (e) indenyl))) zirconium dichloride (105) was activated with MAO to produce i-PP with an activity of $1.0\times10\sp8$ g of PP/(mol of Zr$\rm\cdot\lbrack C\sb3H\sb6\rbrack{\cdot}h)$ and higher isotacticity than that produced by the unbridged analog (100). A new polycyclic ligand, 2-methylbenz (f) indene (111), was synthesized. Attempts to convert 111 into Group 4 organometallic complexes failed, however a rhodium dicarbonyl complex 112 was synthesized. The unsuccessful synthesis of Group 4 complexes was attributed to the loss of resonance stabilization in the proposed pentahapto coordinated complexes.