Investigation of Isomerization and Oxidation-Reduction Reactions of Halotricarbonylbis(diphenylphosphino)methanemanganese(I) Complexes Using Chemical and Electrochemical Techniques

A. M. Bond, R. Colton, M. J. McCormick

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Abstract

Electrochemical and chemical investigations of Mn(CO)3dpmX [dpm = Ph2PCH2PPh2, X = Cl, Br] have allowed the elucidation of the structural, kinetic, and thermodynamic properties of the [Mn(CO)3dpmX]0.+ system. The equilibrium fac-Mn(I) + mer-Mn(II) ⇌ mer-Mn(I) + fac-Mn(II) is shown to lie substantially to the left. The various isomers for this system have all been individually identified and characterized by a variety of physical measurements. Electrochemistry is demonstrated to be particularly valuable in distinguishing the different species as well as providing information about redox properties. The reactions occurring in solution are summarized by the equations [Formula omitted] The most interesting feature of this system is that both mer- and fac-[Mn(CO)3dpmX]+ are low spin, as shown by ESR and direct magnetic susceptibility measurements (mer only). Reduction of Mn(I) (2e) and oxidation of Mn(II) were also observed.

Original languageEnglish
Pages (from-to)155-159
Number of pages5
JournalInorganic Chemistry
Volume16
Issue number1
DOIs
Publication statusPublished - 1 Jan 1977
Externally publishedYes

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