119Sn NMR spectroscopic and structural properties of transition metal complexes with terminal stannylene ligands

被引：27
作者：
Agustin, Dominique [2 ,3 ]
Ehses, Markus [1 ]
机构：
[1] Univ Saarland, Inst Anorgan Chem, D-66123 Saarbrucken, Germany
[2] CNRS, Chim Coordinat Lab, F-31077 Toulouse, France
[3] Univ Toulouse, UPS, IUT A, F-81104 Castres, France
来源：
COMPTES RENDUS CHIMIE | 2009年 / 12卷 / 10-11期
关键词：
Tin; Transition metal complexes; Stannylenes; Sn-119; NMR; Coupling constant; X-ray crystallography; Molecular structure; STANNA-CLOSO-DODECABORATE; TIN HETERODIMETALLIC COMPLEXES; DENSITY-FUNCTIONAL THEORY; SPIN COUPLING-CONSTANTS; RAY CRYSTAL-STRUCTURE; MAIN-GROUP ELEMENTS; SN-FE-SN; MOLECULAR-STRUCTURE; X-RAY; COORDINATION CHEMISTRY;
D O I：
10.1016/j.crci.2009.04.004
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The coordination effect of transition metal TMLn (L = co-ligand) on stannylenes R2SnBn (B = base, n = 0-2) has been examined analysing Sn-119 NMR data and X-ray molecular structures from the literature up to 2008. Coordination deshielding Delta delta (Sn-119) and chemical shift delta (Sn-119) of BnR2Sn-TM(CO)(n) complexes, linearly correlate with delta(Sn-119) of R2Sn. Slope, intercept and typical regions are interpreted through different ratios of sigma/pi-back bonding and impact of TM, R and B, Hybridisation changes explain dependencies of (1)J(Sn-TM) coupling constants on L, R, B-n and TM gyromagnetic ratios gamma(TM). The Sn-TM bond lengths follow a parabolic profile along the TM period, fine-tuned by R, B and L-n Electronic modifications on carbonyl complexes classify R2Sn as poor pi-acceptors, while shortening of Sn-R and widening of angles R-Sn-R correspond to increased s-character of the Sn-TM bond. A "coordinative Lewis base radius" r(coord)(SnR2) of 1.18 angstrom is proposed. To cite this article: D. Agustin, M. Ehses, C R. Chimie 12 2009. (C) 2009 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.
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页码：1189 / 1227
页数：39
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