Theoretical model for insertion of the 16-electron species (eta(5)-C5H5)M(L) into saturated hydrocarbons. A (eta(5)-C5H5)M(CO)+CH4 (M=Ru-, Os-, Rh, Ir, Pd+, Pt+) case study

被引:31
作者
Su, MD
Chu, SY
机构
[1] Department of Chemistry, National Tsing Hua University
关键词
D O I
10.1021/om960837w
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The potential energy surfaces corresponding to the reaction of the 16-electron (eta(5)-C5R5)M(CO) (M = Ru-, Os-, Rh, Ir, Pd+, Pt+) with methane have been investigated by employing the MP2, MP4SDTQ, and B3LYP levels of theory. It is found that a more electron-rich as well as heavier transition-metal center (i,e., the third row) will facilitate the oxidative-addition reactions with alkane C-H bonds. In contrast, a very electron-deficient and a lighter transition metal center (i.e., the second row) will tend. to undergo reductive-elimination reactions of C-H bond forming. A comparison of MP2, MP4, and density functional theory in the CpM(CO) model systems shows that the B3LYP method is able to avoid the multireference problems that ab initio methods have. Nevertheless, the MP2/LANL1DZ method can provide qualitatively correct results.
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页码:1621 / 1627
页数:7
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