DETAILS OF POTENTIAL-ENERGY SURFACES INVOLVING C-C BOND ACTIVATION - REACTIONS OF FE+, CO+, AND NI+ WITH ACETONE

被引：50

作者：

CARPENTER, CJ ^{[1
]}

VANKOPPEN, PAM ^{[1
]}

BOWERS, MT ^{[1
]}

机构：

[1] UNIV CALIF SANTA BARBARA, DEPT CHEM, SANTA BARBARA, CA 93106 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1995年 / 117卷 / 44期

关键词：

D O I：

10.1021/ja00149a021

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Product kinetic energy release distributions (KERDs) for reactions of Fe+, Co+, and Ni+ with acetone to eliminate C2H6 and CO have been measured. These distributions are statistical and are very sensitive to the energy of the rate-limiting transition state, We argue this transition state is most likely due to initial C-C bond insertion. The rate-limiting transition state acts to restrict high angular momentum reactant collision complexes from going on to products, thereby reducing the average kinetic energy released. By modeling the experimental KERDs, the rate-limiting transition state was determined to lie in the range of 9 +/- 3 kcal/mol below the energy of the M(+) + acetone reactants for all three metal ions. Bond energies for M(+)-CO and M(+)-C2H6 have also been determined:D-0(o)(Co+-CO) 39.1 +/- 3 kcal/mol, D-0(o)(Fe+-C2H6) = 17.9 +/- 3 kcal/mol, and D-0(o)(Ni+-C2H6) = 28.7 +/- 3 kcal/mol. In addition, modeling the experimental KERDs indicates that the MC(2)H(6)(+) product formed in the reaction of M(+) with acetone is nearly exclusively an ethane adduct, with a maximum 10-15% of the dimethyl complex being formed. Finally, arguments relating the initial rate-limiting transition state to the C-H bond activation transition state in propane are made and suggest that the C-C bond activation transition state in small alkanes is 6 +/- 5 kcal/mol higher in energy than C-H bond activation.

引用

页码：10976 / 10985

页数：10

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