Dehydrogenation of ethane by CpM+ (M = Fe, Co, Ni) in the gas phase.: An FT-ICR-MS study

被引：25
|
作者：
Ekeberg, D
Uggerud, E
Lin, HY
Sohlberg, K
Chen, HL
Ridge, DP
机构：
[1] Univ Oslo, Dept Chem, N-0315 Oslo 3, Norway
[2] Univ Delaware, Dept Chem & Biochem, Newark, DE 19716 USA
[3] Univ Delaware, Ctr Catalyt Sci & Technol, Newark, DE 19716 USA
来源：
ORGANOMETALLICS | 1999年 / 18卷 / 01期
关键词：
D O I：
10.1021/om980378u
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
CpCo+ and CpNi+ (Cp = eta(5)-C5H5, cyclopentadienyl) dehydrogenate ethane in ion molecule reactions in an FT-ICR-MS cell. CpFe+ does not. The differences in reactivity are rationalized using MO theory. The theoretical calculations show that the electronic structures of the metals in the organometallic complexes are perturbed by the Cp ligand to different degrees. The strong metal 4s character of the LUMOs for CpCo+ and CpNi+ favors the C-H bond activation step, leading to dehydrogenation. Available unoccupied metal 4s orbitals have previously been shown to facilitate C-H and H-H bond activation in reactions with naked metal ions.
引用
收藏
页码：40 / 44
页数：5
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