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. 2000 Sep 18;39(19):4354-7.
doi: 10.1021/ic9910108.

Heterogeneous electron-transfer rate constants for M2(O2CR)4(0)/+, where M = Mo, W, Ru, or Rh and R = alkyl or aryl

M H Chisholm  1 , K C Glasgow, L J Klein, A M Macintosh, D G Peters
Affiliations

Heterogeneous electron-transfer rate constants for M2(O2CR)4(0)/+, where M = Mo, W, Ru, or Rh and R = alkyl or aryl

M H Chisholm et al. Inorg Chem. .

Abstract

By the use of Nicholson's method, the heterogeneous electron-transfer rate constants (ks) for the oxidation of a series of M2(O2CR)4 complexes have been determined in benzonitrile, where the metal M = Mo, W, Ru, or Rh and R = alkyl or aryl. For R = tBu, the values of ks follow the order M = Mo > W > Ru > Rh. No simple influence of R on ks was observed, although added ligands that are known to reversibly bind to the dinuclear center were shown to influence the E1/2 values in order of their basicity and to suppress the rate of electron transfer. The reported data are compared with those obtained for Cp2Fe0/+, Cp2*Fe0/+, and Ru(bpy)2(2)+/3+ and with earlier work on dirhenium multiply bonded compounds.

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