The phosphinoethylsilyl group as a bifunctional chelate. Asymmetric induction at platinum(II)
作者:Rupert D. Holmes-Smith、Stephen R. Stobart、T. Stanley Cameron、Klaus Jochem
DOI:10.1039/c39810000937
日期:——
and its geometry, inferred from 31P n.m.r. data, is confirmed by X-ray crystallography for R1= R2= Me; when R1≠ R2 racemic and meso-diastereomers are formed in varying ratio consistent with asymmetric induction during stepwise chelation to give the rac-complex as the preferred isomer, and this is proven where R1= Me, R2= Ph by diastereomer separation followed by Pt–Si bond-cleavage with (+)-EtCH(Me)-CH2I
报道了顺式-[Pt(PPh 2 CH 2 CH 2 SiR 1 R 2)2 ]的合成,由31 P nmr数据推导,其几何构型由X射线晶体学确定,R 1 = R 2 = Me ; 当R 1 ≠R 2外消旋体和内消旋非对映体的形成比例与逐步螯合过程中的不对称诱导一致时,以rac-复合体为优选异构体,这证明了其中R 1 = Me,R 2=非对映异构体分离后的Ph,然后用(+)-EtCH(Me)-CH 2 I裂解Pt-Si键。