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

doi:10.1021/ja00413a008

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

Research output: Contribution to journal › Article › Research › peer-review

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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 language	English
Pages (from-to)	6827-6832
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	103
Issue number	23
DOIs	https://doi.org/10.1021/ja00413a008
Publication status	Published - Nov 1981
Externally published	Yes

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

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.",

author = "Bond, \{A. M.\} and Darensbourg, \{D. J.\} and E. Mocellin and Stewart, \{B. J.\}",

year = "1981",

month = nov,

doi = "10.1021/ja00413a008",

language = "English",

volume = "103",

pages = "6827--6832",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "23",

}

Electrochemical Investigations of Compounds Having Isomeric Forms with Similar Standard Redox Potentials: Oxidation of Bis(tri-n-butylphosphine)molybdenum Tetracarbonyl and Related Complexes. / Bond, A. M.; Darensbourg, D. J.; Mocellin, E. et al.
In: Journal of the American Chemical Society, Vol. 103, No. 23, 11.1981, p. 6827-6832.

Research output: Contribution to journal › Article › Research › peer-review

TY - JOUR

T1 - Electrochemical Investigations of Compounds Having Isomeric Forms with Similar Standard Redox Potentials

T2 - Oxidation of Bis(tri-n-butylphosphine)molybdenum Tetracarbonyl and Related Complexes

AU - Bond, A. M.

AU - Darensbourg, D. J.

AU - Mocellin, E.

AU - Stewart, B. J.

PY - 1981/11

Y1 - 1981/11

N2 - 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.

AB - 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.

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

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