Electrochemical Investigations of Compounds Having Isomeric Forms with Similar Standard Redox Potentials: Oxidation of Bis(tri-n-butylphosphine)molybdenum Tetracarbonyl and Related Complexes

A. M. Bond, D. J. Darensbourg, E. Mocellin, B. J. Stewart

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Abstract

The electrochemical oxidation or reduction of compounds existing in isomeric forms can be accompanied by conversions from one structural form to another. If the isomeric forms have similar standard redox potentials, structural rearrangements can be difficult to detect. Thus, the electrochemistry of compounds having isomeric forms, while frequently appearing to be deceptively simple, can be extremely complicated. Mo(CO)4(P-n-Bu3)2 can exist in cis and trans isomeric forms and the trans+/trans° and cis+/cis° standard redox potentials are similar. This and related systems such as Mo(CO)4(PEt3)2 and Mo(CO)4(PPh3)2 are therefore used to provide examples which illustrate the interactions that may need to be considered. Importantly, it is demonstrated that structural rearrangements of these kind occurring via an intramolecular mechanism do not lead to the observation of slow electron transfer.

Original languageEnglish
Pages (from-to)6827-6832
Number of pages6
JournalJournal of the American Chemical Society
Volume103
Issue number23
DOIs
Publication statusPublished - Nov 1981
Externally publishedYes

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