The metal-carbon bond in vinylidene, carbonyl, isocyanide and ethylene complexes

被引：19

作者：

Moigno, D

Callejas-Gaspar, B

Gil-Rubio, J

Werner, H

Kiefer, W

机构：

[1] Univ Wurzburg, Inst Phys Chem, D-97074 Wurzburg, Germany

[2] Univ Wurzburg, Inst Anorgan Chem, D-97074 Wurzburg, Germany

[3] Univ Murcia, Dept Quim Inorgan, E-30011 Murcia, Spain

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2002年 / 661卷 / 1-2期

关键词：

DFT-calculations; FT-Raman spectroscopy; metal-carbon bond; isotopic substitution; vinylidene complexes; rhodium; tungsten; trans influence;

D O I：

10.1016/S0022-328X(02)01851-X

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Density functional theory (DFT) calculations were carried out for trans -[RhX(L)(PMe3)(2)] (L=C=CH2, C=CHC6H5, CO, 2,6-Me2C6H3NC, C2H4) which served as model compounds for the analysis of the vibrational spectra of related complexes. The characterization of the metal-carbon stretching mode allowed to study the trans influence of a series of ligands on the metalcarbon bond in vinylidene, carbonyl and isocyanide complexes. Furthermore, the comparison of the FT-Raman spectra of the complexes trans-[RhF(CO)(PiPr(3))(2)] and trans-[RhF(C-13=(CH2)-C-13)(PiPr(3))(2)] which possess the same reduced mass (C-13=(CH2)-C-13 vs. CO) allowed for an evaluation of the Rh-C bond strength free of any mass effects and therefore only showing effects of electronic nature. (C) 2002 Elsevier Science BN. All rights reserved.

引用

页码：181 / 190

页数：10

共 60 条

[1] AB-INITIO MOLECULAR-ORBITAL STUDY OF SUBSTITUENT EFFECTS IN VASKA TYPE COMPLEXES (TRANS-IRL(2)(CO)X) - ELECTRON-AFFINITIES, IONIZATION-POTENTIALS, CARBONYL STRETCH FREQUENCIES, AND THE THERMODYNAMICS OF H-2 DISSOCIATIVE ADDITION [J].