Theoretical study of the rhenium-alkane interaction in transition metal-alkane sigma-complexes.

Cobar, Erika A; Khaliullin, Rustam Z; Bergman, Robert G; Head-Gordon, Martin · Proc Natl Acad Sci U S A · 2007

basic_science · Level V

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Abstract

Metal-alkane binding energies have been calculated for [CpRe(CO)2](alkane) and [(CO)2M(C5H4)C[triple bond]C(C5H4)M(CO)2](alkane), where M = Re or Mn. Calculated binding energies were found to increase with the number of metal-alkane interaction sites. In all cases examined, the manganese-alkane binding energies were predicted to be significantly lower than those for the analogous rhenium-alkane complexes. The metal (Mn or Re)-alkane interaction was predicted to be primarily one of charge transfer, both from the alkane to the metal complex (70-80% of total charge transfer) and from the metal complex to the alkane (20-30% of the total charge transfer).

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