N–N Bond Cleavage of 1,2-Diarylhydrazines and N–H Bond Formation via H-Atom Transfer in Vanadium Complexes Supported by a Redox-Active Ligand
作者： Carsten Milsmann , Scott P. Semproni , Paul J. Chirik
DOI: 10.1021/JA5062196
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摘要: Addition of stoichiometric quantites 1,2-diarylhydrazines to the bis(imino)pyridine vanadium dinitrogen complex, [{(iPrBPDI)V(THF)}2(μ2-N2)] (iPrBPDI = 2,6-(2,6-iPr2-C6H3N═CPh)2C5H3N), resulted in N–N bond cleavage yield corresponding bis(amido) derivatives, (iPrBPDI)V(NHAr)2 (Ar Ph, Tol). Spectroscopic, structural, and computational studies support an assignment as vanadium(III) complexes with chelate radical anions, [BPDI]•–. With excess 1,2-diarylhydrazine, formation imide amide compounds, (iPrBPDI)V(NHAr)NAr, were observed along aryldiazene aniline. A DFT-computed N–H dissociation free energy 69.2 kcal/mol was obtained for (iPrBPDI)V(NHPh)NPh, interconversion between this compound (iPrBPDI)V(NHPh)2 (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (TEMPO), 1,2-diphenylhydrazine, xanthene experimentally bracketed value 67.1 73.3 kcal/mol. For (iPrBPDI)V(NHPh)2, BDFE DFT-cal...
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