Substitution and Isomerization of Asymmetric β-Diketonato Rhodium(I) Complexes: A Crystallographic and Computational Study

被引：25

作者：

Hopmann, Kathrin H. ^{[1
,2
]}

Stuurman, Nomampondomise F. ^{[3
]}

Muller, Alfred ^{[4
]}

Conradie, Jeanet ^{[1
,2
,3
]}

机构：

[1] Univ Tromso, Ctr Theoret & Computat Chem, N-9037 Tromso, Norway

[2] Univ Tromso, Dept Chem, N-9037 Tromso, Norway

[3] Univ Orange Free State, Dept Chem, ZA-9300 Bloemfontein, South Africa

[4] Univ Johannesburg, Dept Chem, ZA-2006 Johannesburg, South Africa

来源：

ORGANOMETALLICS | 2010年 / 29卷 / 11期

基金：

新加坡国家研究基金会;

关键词：

IODOMETHANE OXIDATIVE ADDITION; EFFECTIVE CORE POTENTIALS; CRYSTAL-STRUCTURE; TRANS ISOMERIZATION; MONOCARBONYLPHOSPHINE COMPLEXES; MOLECULAR CALCULATIONS; IR SPECTROPHOTOMETRY; REACTION-MECHANISM; NMR-SPECTROSCOPY; UTILIZING UV/VIS;

D O I：

10.1021/om1000138

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Ligand substitution of PPh3 for CO in the asymmetric square-planar beta-diketonato complex [Rh(PhCOCHCOCH2CH3)(CO)(2)] leads to formation of the monosubstituted [Rh(PhCOCHCOCH2CH3)(CO)(PPh3)] product. Two geometrical product isomers are possible, which unexpectedly crystallize in the same crystal lattice. DFT calculations of the substitution reaction support a twostep mechanism, involving temporary dissociation of a beta-diketonato ligand and formation of a square-planar intermediate. Analysis of the mechanisms involved in product isomerization suggests several noncatalyzed and solvent-assisted interconversion pathways.

引用

页码：2446 / 2458

页数：13

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