O/C bond cleavage of CO2 by NiI

被引:25
作者
Fullmer, Benjamin C.
Fan, Hongjun
Pink, Maren
Caulton, Kenneth G. [1 ]
机构
[1] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA
关键词
D O I
10.1021/ic701843u
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Reaction of (PNP)Ni, where PNP is [((Bu2PCH2SiMe2)-Bu-t)(2)N](-1), with CO2 occurs rapidly even at -60 degrees C to form exclusively the product of transposition of the amide N and one CO2 oxygen: [((Bu2PCH2)-Bu-t SiMe2)(2)O]Ni(NCO). DFT(B3LYP) evaluation of several candidate intermediates for breaking two Si/N and one C/O bond and forming two Si/O and one N/C bond reveal species at and below the energy of the separated particles, and establish, the location of the spin densities in each.
引用
收藏
页码:1865 / 1867
页数:3
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