Mechanistic Aspects of the Alternating Copolymerization of Propene with Carbon Monoxide Catalyzed by Pd(II) Complexes of Unsymmetrical Phosphine−Phosphite Ligands
作者： Kyoko Nozaki , Naomasa Sato , Yoichi Tonomura , Masako Yasutomi , Hidemasa Takaya
DOI: 10.1021/JA973199X
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摘要: The reaction steps responsible for the highly enantioselective asymmetric copolymerization of propene with carbon monoxide catalyzed by a cationic Pd(II) complex bearing an unsymmetrical chiral bidentate phosphine−phosphite, (R,S)-BINAPHOS [(R,S)-2-(diphenylphosphino)-1,1‘-binaphthalen-2‘-yl 1,1‘-binaphthalene-2,2‘-diyl phosphite = L1], have been studied. Stepwise identification and characterization were carried out catalyst precursors (SP-4-2)- (SP-4-3)-Pd(CH3)Cl(L1) (1a 1b) (SP-4-3)-[Pd(CH3)(CH3CN)(L1)]·X1 (X1 B{3,5-(CF3)2C6H3}4) (2), complexes related to steps, (SP-4-3)-[Pd(COCH3)(CH3CN)(L1)]·X1 (3), (SP-4-3)- (SP-4-4)-[Pd{CH2CH(CH3)COCH3}(L1)]·X1 (4a 4b), (SP-4-3)-[Pd{COCH2CH(CH3)COCH3}(CH3CN)(L1)]·X1 (5), (SP-4-3)-[Pd{CH2CH(CH3)COCH2CH(CH3)COCH3}(L1)]·X1 (6). An X-ray structure alkyl 4a has obtained. Studies on [Pt(CH3)2(L1)] (8) reveal that methyl group is more stabilized at position trans phosphine than cis position....
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