Estimating the (CO)5Cr-(η2-benzene) bond dissociation enthalpy:: reaction of the (CO)5Cr(η2-benzene) complex with a series of (CH3)nTHF (n = 0, 1, 2, and 4) ligands

被引:12
作者
Bengali, AA [1 ]
Stumbaugh, TF [1 ]
机构
[1] Dickinson Coll, Dept Chem, Carlisle, PA 17013 USA
关键词
D O I
10.1039/b210575f
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The displacement of the benzene ligand from the photolytically generated (CO)(5)Cr(eta(2)-benzene) complex by THF and a series of methyl substituted (CH(3))(n)THF (n = 1, 2, and 4) ligands was studied using the technique of laser flash photolysis. The data suggest that two independent pathways (D and I(d)) contribute to the overall displacement of the benzene solvent from the Cr center. The contribution of the I(d) pathway increases as the steric bulk of the Me(n)THF ligand is reduced from Me(4)THF to MeTHF. The activation enthalpy of 11.4 +/- 1.1 kcal mol(-1) obtained when the entering ligand is Me(4)THF is considered to be a lower estimate of the (CO)(5)Cr-(eta(2)-benzene) bond dissociation enthalpy. A detailed energetic profile of the substitution reaction is presented.
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页码:354 / 360
页数:7
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