Coupled Two-Electron/Halide Transfer Reactions of Ruthenoceniums and Osmoceniums

Inorganic Chemistry

Volumn 35, Issue 26, 1996, Pages 7699-7703

  Shea, Timothy M ^a   Deraniyagala, Samitha P ^a,b   Studebaker, Daniel B ^a   Westmoreland, T David ^a  

^a WESLEYAN UNIVERSITY   (United States)

^b UNIVERSITY OF SRI JAYEWARDENEPURA   (Sri Lanka)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0343457706     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic961000w     Document Type: Article

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55. Cl is typically ∼0.65 for terminal halide complexes and ∼0.5 for bridging halides. This ratio and the relative masses of the halides suggest that the intramolecular reorganization energy for iodide may, in fact, be as much as 1.5 times that for chloride, (a) Clark, R. J. H.; Williams, C. S. Inorg. Chem. 1965, 4, 350-357. (b) Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordination Compounds, 4th ed; John Wiley and Sons: New York, 1986.
56. Cl is typically ∼0.65 for terminal halide complexes and ∼0.5 for bridging halides. This ratio and the relative masses of the halides suggest that the intramolecular reorganization energy for iodide may, in fact, be as much as 1.5 times that for chloride, (a) Clark, R. J. H.; Williams, C. S. Inorg. Chem. 1965, 4, 350-357. (b) Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordination Compounds, 4th ed; John Wiley and Sons: New York, 1986.
57. III intermediate, we have assumed that there are no minima along the reaction coordinate other than the reactant and product states. If an intermediate does exist, it is only weakly stabilized relative to the transition state. Further, we cannot at this point completely rule out a metal-metal-bonded dimeric transition state with bridging halide, but this possibility seems unlikely on the basis of steric constraints and the net decrease in bond order in the transition state.
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