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Substitution and Insertion Reactions

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Book cover Mechanisms of Inorganic and Organometallic Reactions

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Abstract

The principle of microscopic reversibility as applied to the kinetics and mechanism of ligand substitution on [Mn(CO)5X] has been reviewed. It is concluded that two stereo chemically rigid (k12 = k21 = 0) intermediates [M(CO)4X] are involved with k1 ≫ k2 (Scheme 1). The author states that, contrary to previous statements, the principle of microscopic reversibility does not require that the addition of CO to these intermediates follow exactly the same degree of preference as does the dissociation of CO to form these intermediates.(l) However, Brown has refuted these arguments in a recent submission. (2) It is his conclusion that a large cis labilization (k1 ≫ k2), coupled with a low-energy process which allows the exchange of at least some of the CO ligands in the five-coordinate intermediate (k12 and k21 ≠ 0), accounts for the most reliable experimental data.

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    M. V. Twigg

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© 1989 Plenum Press, New York

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Twigg, M.V. (1989). Substitution and Insertion Reactions. In: Twigg, M.V. (eds) Mechanisms of Inorganic and Organometallic Reactions. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-0827-0_10

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