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Published June 1, 1994 | public
Journal Article Open

Model Ziegler-Natta α-Olefin Polymerization Catalysts Derived from [{(η^5-C_5Me_4)SiMe_2(η^1-NCMe_3)}(PMe_3)Sc(µ_2-H)]_2 and [{(η^5-C_5Me_4)SiMe_2(η^1-NCMe_3)}Sc(µ_2-CH_2CH_2CH_3)]_2. Synthesis, Structures, and Kinetic and Equilibrium Investigations of the Catalytically Active Species in Solution


The scandium hydride complex [(Cp*SiNR)(PMe_3)Sc(µ-H)]_2 (1), ((Cp*SiNR) = ((η^5-C_5Me_4)SiMe_2(η^1-NCMe_3)}) is prepared by hydrogenation of (Cp*SiNR)ScCH(SiMe_3)_2 in the presence of trimethylphosphine. The hydride complex is a catalyst precursor for the polymerization of α-olefins, yielding atactic products of low molecular weight (M, = 3000-7000). GC/MS analysis of volatile, oligomeric products revealed that all scandium centers are active during the polymerization. Selectivity for head-to-tail insertion is high (>99%) and for the tetramer, pentamer, and hexamer formed during propene polymerization, the maximum theoretical numbers of head-to-tail stereoisomers are observed by capillary GC. The stoichiometric reaction between 1 and 2 equiv of ethylene produces the unusual ethylene-bridged dimer [(Cp*SiNR)(PMe_3)Sc]_2(µ,η^2,η^2-C_2H_4) (2) and an equivalent of ethane, whereas the same reaction with propene affords the phosphine-free, alkyl-bridged scandium dimer [(Cp*S~NR)Sc]_2(µ-CH_2CH_2CH_3)_2 (3). The absence of coordinating phosphine allows the latter complex to function as a more active olefin polymerization catalyst precursor. 1 reacts with styrene to form a unique double-insertion product arising from sequential 1,2- and 2,1-styrene insertion. The structure of the catalytic intermediate in solution was determined by low-temperature ^(13)C-NMR studies of the model complexes (Cp*SiNR)(P(^(13)CH_3)_3]ScCH_2CH(CH_3)CHCH_2CH_2CH_3 and (Cp*SiNR)(PMe_3)Sc^(13)CH_2CHCH(^(13)CH_3)_2. One phosphine-bound species is observed in equilibrium with only one phosphine-free species. The symmetry properties of the latter indicate that it is a monomeric, hence 12-electron, scandium alkyl complex. Semiquantitative treatment of equilibrium concentration data supports this conclusion.

Additional Information

© 1994 American Chemical Society. Received November 18, 1993. This work has been supported by USDOE Office of Basic Energy Sciences (Grant No. DE-FG03-85ER113431) and by Exxon Chemicals America.

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Supplemental Material - ja00090a011_si_001.pdf

Supplemental Material - ja4623.pdf


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August 20, 2023
August 20, 2023