Modulation of molybdenum-centered redox potentials and electron-transfer rates by sulfur versus oxygen ligation

Temperature-dependent measurements of potential, E degrees', and electron-transfer rate constant, k(s,h), are reported for electrochemical reduction (in 0.3 M TBAPF(6)/CH(3)CN) of a series of oxomolybdenum(V) complexes, [(Tp)MoO(X,Y)], where Tp = hydrotris(3,5-dimethyl-1-pyrazolyl)borate and X,Y is a series of bidentate 1,2-disubstituted aliphatic or aromatic ligands in which oxygen donors are replaced sequentially by sulfur. E degrees' values shift in the positive direction, and k(s,h) values increase as O is replaced by S and as the framework of the ligand is changed from aliphatic to aromatic. The electrochemical enthalpy of activation, measured under conditions of zero driving force as DeltaH= -R partial differential[ln(k(s,h))]/ partial differential(1/T) and corrected for an outer-shell component by the mean spherical approximation, is approximately 10 kJ mol(-1) larger for complexes with O versus S donors and with an aliphatic versus aromatic ligand framework. Thus, the rate of Mo(V/IV) electron transfer is modulated primarily by differences in inner-shell reorganization. Following a recent description of electronic structure contributions to electron-transfer reactivity (Kennepohl, P.; Solomon, E. I. Inorg. Chem. 2003, 42, 679 ff), it is concluded that more effective charge distribution over the entire molecular structure, as mediated by electronic relaxation in S versus O and aromatic versus aliphatic systems, is responsible for the influence of ligand structure on the kinetics and thermodynamics of Mo-centered electron transfer. There is no evidence, based on experimentally measured pre-exponential factors, that sulfur donors or an aromatic ligand framework are more effective than their structural counterparts in facilitating electronic coupling between the electrode and the Mo d(xy) redox orbital.