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.
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页码：2446 / 2458
页数：13
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