Synthesis and reversible reductive coupling of cationic, dinitrogen-derived diazoalkane complexes.
A series of cationic diazoalkane complexes [4-RC(6)H(4)C(H)NNMo(N[t-Bu]Ar)(3)][AlCl(4)], [1-R][AlCl(4)] (R = NMe(2), Me, H, Br, CN; Ar = 3,5-C(6)H(3)Me(2)) has been prepared by treatment of the N(2)-derived diazenido complex Me(3)SiNNMo(N[t-Bu]Ar)(3) with 4-RC(6)H(4)CHO and 2 equiv of AlCl(3). The structures of [1-H][AlCl(4)] and [1-NMe(2)][AlCl(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][AlCl(4)] was shown to be linear with the Hammett sigma parameter. This reduction process forms the C-C bonded dimer, mu-(4-RC(6)H(4)C(H)NN)(2)[Mo(N[t-Bu]Ar)(3)](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-RC(6)H(4)C(H)NNMo(N[t-Bu]Ar)(3), 1-R, that is an intermediate in the formation of [1-R](2). The C-C bond in [1-R](2) is redox-noninnocent and is broken upon oxidation. This reaction was used to prepare [1-H][A] (A = PF(6)(-), OTf(-)), and possible uses of this property in charge-storage devices are discussed.
Curley
John J
JJ
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Room 6-435, Cambridge, Massachusetts 02139, USA.
Murahashi
Tetsuro
T
Cummins
Christopher C
CC