The Effects of Donor-Acceptor Electronic Interactions on the Rates of Gas-Phase Metallocene Electron-Exchange Reactions
PURDUE UNIV LAFAYETTE IN DEPT OF CHEMISTRY
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Rate constants for electron self exchange, kax, of five cobaltocenium-cobaltocene and ferrocenium-ferrocene couples in the gas phase have been measured by means of Fourier transform ion cyclotron resonance mass spectrometry in order to explore the possible effects of donor-acceptor electronic coupling on gas-phase redox reactivity. The systems studied were selected in view of the substantial variations in electronic coupling inferred on the basis of their solvent-dependent reactivities and on theoretical grounds. The sequence of kax values determined in the gas phase is roughly similar to that observed in solution, although the magnitude of the kax variations is smaller in the former case. The likely origins of these differences in gas-phase reactivity are discussed in light of the known variations in the electronic coupling matrix element H12, inner-shell reorganization energy.
- Physical Chemistry