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Chisholm MH, D'Acchioli JS, Pate BD, et al. Cations M2(O2CtBu)4+, where M = Mo and W, and MoW(O2CtBu)4+. Theoretical, spectroscopic, and structural investigations. Inorg Chem. 2005;44(4):1061-7doi: 10.1021/ic049081g.
Chisholm, M. H., D'Acchioli, J. S., Pate, B. D., Patmore, N. J., Dalal, N. S., & Zipse, D. J. (2005). Cations M2(O2CtBu)4+, where M = Mo and W, and MoW(O2CtBu)4+. Theoretical, spectroscopic, and structural investigations. Inorganic chemistry, 44(4), 1061-7. https://doi.org/10.1021/ic049081g
Chisholm, Malcolm H, et al. "Cations M2(O2CtBu)4+, where M = Mo and W, and MoW(O2CtBu)4+. Theoretical, spectroscopic, and structural investigations." Inorganic chemistry vol. 44,4 (2005): 1061-7. doi: https://doi.org/10.1021/ic049081g
Chisholm MH, D'Acchioli JS, Pate BD, Patmore NJ, Dalal NS, Zipse DJ. Cations M2(O2CtBu)4+, where M = Mo and W, and MoW(O2CtBu)4+. Theoretical, spectroscopic, and structural investigations. Inorg Chem. 2005 Feb 21;44(4):1061-7. doi: 10.1021/ic049081g. PMID: 15859287.
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Inorg Chem. 2005 Feb 21;44(4):1061-7. doi: 10.1021/ic049081g.

Cations M2(O2CtBu)4+, where M = Mo and W, and MoW(O2CtBu)4+. Theoretical, spectroscopic, and structural investigations.

Inorganic chemistry

Malcolm H Chisholm, Jason S D'Acchioli, Brian D Pate, Nathan J Patmore, Naresh S Dalal, David J Zipse

Affiliations

  1. Department of Chemistry, The Ohio State University, Columbus, Ohio 43210-1185, USA. [email protected]

PMID: 15859287 DOI: 10.1021/ic049081g

Abstract

With the aid of density function theory, the molecular and electronic structures of the molecules Mo2(O2CMe)4, MoW(O2CMe)4, and W2(O2CMe)4 and their single-electron oxidized radical cations have been determined; this includes calculated observables such as v(MM) and the delta --> delta* electronic transition energies. The calculated properties are compared with those for the corresponding pivalates, M2(O2CtBu)4 (M = Mo or W) and MoW(O2CtBu)4 and their radical cations prepared in situ by oxidation with Cp2FePF6. The EPR spectra of the radical cations are also reported. The EPR spectrum of the MoW(O2CtBu)4+ cation reveals that the unpaired electron is in a polarized MM delta orbital having 70% Mo and 30% W character. The MM stretching frequencies show good correlation with the MM bond lengths obtained from single-crystal X-ray diffraction studies of MoW(O2CtBu)4, W2(O2CtBu)4, and W2(O2CtBu)4+PF6- compounds, along with previously reported structures. These data provide benchmark parameters for valence trapped dicarboxylate bridged radical cations of the type [(tBuCO2)3M2]2(micro-O2C-X-CO2)+ (X = conjugated spacer).

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