Structure and facile unimolecular twist-rotation of cis-bis(silyl)bis(phosphine)platinum and cis-bis(stannyl)bis(phosphine)palladium complexes

被引：54

作者：

Tsuji, Y ^{[1
]}

Nishiyama, K ^{[1
]}

Hori, S ^{[1
]}

Ebihara, M ^{[1
]}

Kawamura, T ^{[1
]}

机构：

[1] Gifu Univ, Fac Engn, Dept Chem, Gifu 5011112, Japan

来源：

ORGANOMETALLICS | 1998年 / 17卷 / 04期

关键词：

D O I：

10.1021/om970957j

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The structures and fluxional behavior of two cis-bis(silyl)bis(phosphine)platinum complexes (2), cis-[Pt(SiPh2Me)(2)(PMe2Ph)(2)] (2a) and cis-[Pt(SiFMe2)(2)(PEt3)(2)] (2b), and two cis-bis(stannyl)bis(phosphine)palladium complexes (3), cis-[Pd(SnMe3)(2)(PMe3)(2)] (3a) and cis-[Pd(SnMe3)(2)(PMePh2)(2)] (3b), were examined. The molecular structures of 2a and 3a were determined by X-ray crystallographic analysis. The complexes have twisted square-planar structures with cis-orientation of the ligands. The bis(silyl)platinum complexes, 2a and 2b, show fluxional behavior on the NMR time scale. In the fluxional process, the spin-spin coupling between P, Si, and Pt is retained; namely these nuclear spin states are intramolecularly conserved. The fluxionality of 2a and 2b is attributed to unimolecular twist-rotation via a pseudotetrahedral transition state. Similar fluxionality of the bis(stannyl)palladium complex, 3b, is evident by utilizing both solution-and solid-state P-31 NMR.

引用

页码：507 / 512

页数：6

共 58 条

[1] DYNAMIC STEREOCHEMISTRY OF CIS-[PTH(SIR3)(PPH3)2] - SPONTANEOUS LIGAND INTERCHANGE WITH RETENTION OF NUCLEAR-SPIN SPIN CORRELATION [J].