Synthesis and Reversible Reductive Coupling of Cationic, Dinitrogen-Derived Diazoalkane Complexes
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Author(s)
Curley, John J.
Murahashi, Tetsuro
Cummins, Christopher C.
Date Issued
June 2009
Journal
Inorganic Chemistry
Publisher
American Chemical Society
Citation
Curley, John J., Tetsuro Murahashi, and Christopher C. Cummins. “Synthesis and Reversible Reductive Coupling of Cationic, Dinitrogen-Derived Diazoalkane Complexes.” Inorganic Chemistry 48.15 (2009) : 7181-7193. Copyright © 2009 American Chemical Society
Version
Author's final manuscript
Abstract
A series of cationic diazoalkane complexes [4-RC6H4C(H)NNMo(N[t-Bu]Ar)3][AlCl4] 4-RC subscript 6 H subscript 4 C(H)NNMo(N[t-Bu]Ar) subscript 3] [AlCl subscript 4]], [1-R][AlCl4] (R = NMe2, Me, H, Br, CN; Ar = 3,5-C6H3Me2) [[1-R][AlCl subscript 4] (R = NMe subscript 2, Me, H, Br, CN; Ar = 3,5-C subscript 6 H subscript 3 Me subscript 2)] has been prepared by treatment of the N2-derived [N subscript 2 derived] diazenido complex Me3SiNNMo(N[t-Bu]Ar)3 [Me subscript 3 SiNNMo(N[t-Bu]Ar) subscript 3] with 4-RC6H4CHO [4-RC subscript 6 H subscript 4 CHO] and 2 equiv of AlCl3 [AlCl subscript 3]. The structures of [1-H][AlCl4] [AlCl subscript 4] and [1-NMe2][AlCl4] [[1-NMe subscript 2][AlCl subscript 4]were determined by X-ray crystallography. The C−N and N−N stretching modes were identified by a combined IR and Raman spectroscopy study, and other physical properties are discussed in detail. The electrochemical reduction potential for [1-R][AlCl4] [AlCl subscript 4] was shown to be linear with the Hammett σ [delta] parameter. This reduction process forms the C−C bonded dimer, [μ-(4-RC6H4C(H)NN)2[Mo(N[t-Bu]Ar)3]2 [μ [mu]-(4-RC subscript 6 H subscript 4 C(H)NN) subscript 2 [Mo(N[t-Bu]Ar) subscript 3] subscript 2], that was characterized by X-ray crystallography for R = H. Possible mechanisms for the formation of this dimer are presented. Both electrochemical investigations and quantum chemical calculations are used to describe the odd-electron complex 4-RC6H4C(H)NNMo(N[t-Bu]Ar)3 [4-RC subscript 6 H subscript 4 C(H)NNMo(N[t-Bu]Ar) subscript 3], 1-R, that is an intermediate in the formation of [1-R]2 [[1-R] subscript 2]. The C−C bond in [1-R]2 [[1-R] subscript 2] is redox-noninnocent and is broken upon oxidation. This reaction was used to prepare [1-H][A] (A = PF6−, OTf−) [(A = PF subscript 6-,OTf-)], and possible uses of this property in charge-storage devices are discussed.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/ic900495s
