A novel mechanism for the fluxional behaviour of [Pd(η2-tetramethylethylenetetracarboxylate)(2-methylthiomethylpyridine)]

被引：22

作者：

Canovese, L

Lucchini, V

Santo, C

Visentin, F

Zambon, A

机构：

[1] Univ Venice, Dipartimento Sci Ambientali, I-30123 Venice, Italy

[2] Univ Venice, Dipartimento Chim, I-30123 Venice, Italy

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2002年 / 642卷 / 1-2期

关键词：

palladium-olefin complex; dynamic NMR; sulfur inversion mechanism; dimeric C-s intermediate mechanism;

D O I：

10.1016/S0022-328X(01)01197-4

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The fluxional behaviour of [Pd(eta(2)-tmetc)(N-SMe) (tmetc = tetramethylethylenetetracarboxylate, N-SMe = 2-methylthiomethylpyridine) in CD2Cl2 is governed by two mechanisms: (i) the concentration independent inversion at sulfur which averages the methylenic signals and collapses the four methyl signals of tmetc to two; (ii) the concentration dependent mechanism occurring via a dimeric intermediate with C-s symmetry which collapses the two residual tmetc signals into a singlet. (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：58 / 63

页数：6

共 15 条

[1] PLATINUM METAL-COMPLEXES OF POTENTIALLY CHELATING ALKENE THIOETHER AND SELENOETHER LIGANDS - THE SYNTHESIS AND DYNAMIC NUCLEAR MAGNETIC RESONANCE STUDY OF [MX2(E[(CH2)NCR=CR2]2)] (M = PT OR PD - X = CL, BR, OR I - E = S OR SE - N = 2 OR 3 - R = H OR ME) AND THE X-RAY CRYSTAL-STRUCTURE OF CIS-DI-IODO-(5-THIANONA-1,8-DIENE)PLATINUM(II), [PTI2(S[(CH2)2CH=CH2]2)]P [J].