Calculation of Transition Metal Compounds Using an Extension of the CNDO 
Formalism, III. Application to the CO-insertion Reaction as an Example for 
Mechanistic Studies

Saddei, D.; Freund, Hans-Joachim; Hohlneicher, G.

doi:10.1016/S0022-328X(00)93818-X

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Calculation of Transition Metal Compounds Using an Extension of the CNDO Formalism, III. Application to the CO-insertion Reaction as an Example for Mechanistic Studies

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Saddei, D., Freund, H.-J., & Hohlneicher, G. (1980). Calculation of Transition Metal Compounds Using an Extension of the CNDO Formalism, III. Application to the CO-insertion Reaction as an Example for Mechanistic Studies. Journal of Organometallic Chemistry, 186(1), 63-75. doi:10.1016/S0022-328X(00)93818-X.

Cite as: https://hdl.handle.net/21.11116/0000-000E-829B-0

Abstract

An extended version of the CNDO formalism is used to study the mechanism of the CO insertion as an example of intra-molecular insertion reactions which take place in the ligand sphere of a transition metal atom. It is shown that charge density and bond order arguments can explain the experimental facts on a whole class of compounds: Mn(CO)₅R with R = H, CH₃, C₂H₅, CHO, CH₂F, CF₃. The mechanism is predicted to be an R migration. The sequence of the reaction rates is correctly given, and especially the strong inhibition of the reaction by increasing fluorination of the substituent. The reversibility of the reaction is also considered. In the case of Mn(CO)₅C₂H₅ a possible side reaction by abstraction of β-hydrogen instead of alkyl migration is expected, and actually found experimentally.