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6937formation of *py', though energetically less favorable, is faster than formation of py'. In the case of back reactions, the lowest electronic excited states of Irz and py+ are too energetic to be formed in recombination reactions, and inverted behavior is observed.Regardless of the disparity between the *ET and bET reactions, our data demonstrate that inverted driving-force effects can be observed in bimolecular ET reactions. The appearance of inverted effects only for bET reactions may be a feature common to many of the other bimolecular ET systems that have been studied. If formation of electronically excited products is indeed the reason for this disparity, then it should be possible to select donors and acceptors that exhibit inverted driving-force effects in bimolecular photoinduced ET reactions as well. Need).A number of metal complexes containing chloro-, bromo-or iodocarbons ligated through the halide atom have been prepared and, in several instances, characterized by X-ray diffraction.'S2 While many of these complexes involve chelation of a bound ligand, it is evident that coordination of a haloalkane in an intermolecular fashion is possible. ODriscoll and Simon have shown that coordination of an alkyl halide to a transition metal complex is a rapid process, complete within 5 ns of light ab~orption.~ Recent gas-phase studies by Bogdan, Wells, and Weitz have found that the CI-W bond strength in ClFzCCI-W(CO)5 is 19.7 * 0.6

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