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Electron‐Transfer reactions of organometallic and coordination compounds in the absence of solvent: Experimental results and theoretical approaches
Author(s) -
Sharpe Paul,
Christ Charles S.,
Eyler John R.,
Richardson David E.
Publication year - 1988
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560340864
Subject(s) - chemistry , electron transfer , fourier transform ion cyclotron resonance , molecule , metallocene , ferrocene , ion cyclotron resonance , group 2 organometallic chemistry , computational chemistry , resonance (particle physics) , ion , chemical physics , organic chemistry , polymerization , atomic physics , cyclotron , physics , electrode , electrochemistry , polymer
The kinetics of gas‐phase electron transfer reactions for a variety of metal‐containing reactants have been studied by using Fourier transform ion cyclotron resonance mass spectrometry. Classes of ion/molecule processes studied include both self‐exchange (thermoneutral) and exoergic cross reactions. The molecules investigated include metallocenes and octahedral coordination complexes of the transition elements. In a few cases, direct comparisons of condensed‐phase and gas‐phase reactivities can be made. The experiments with octahedral coordination complexes are the first studies of Werner‐type metal complexes in electron‐transfer reactions in the gas phase. Simple theoretical models involving unimolecular rate theory, classical reorganization barriers, and quantum mechanical approaches are used to rationalize the dependence of the overall rates of these reactions on the molecular properties of the reactants. In particular, the role of Franck–Condon factors in charge‐transfer reactions is examined, and theoretically estimated factors are compared with experiment for a typical metallocene, ferrocene.