Transition-metal-mediated reduction and reversible double-cyclization of cyanuric triazide to an asymmetric bitetrazolate involving cleavage of the six-membered aromatic ring |
| |
| Authors: | Shivaiah Vaddypally Vitaly G Kiselev Alex N Byrne C Franklin Goldsmith Michael J Zdilla |
| |
| Institution: | Temple University, 1901 N. 13th St., Philadelphia PA 19122 USA.; School of Engineering, Brown University, 184 Hope St., Providence RI 02912 USA.; Novosibirsk State University, 1 Pirogova Str., 630090 Novosibirsk Russia ; Institute of Chemical Kinetics and Combustion SB RAS, 3 Institutskaya Str., 630090 Novosibirsk Russia ; Semenov Federal Research Center for Chemical Physics RAS, 4 Kosygina Str., 119991 Moscow Russia |
| |
| Abstract: | Cyanuric triazide reacts with several transition metal precursors, extruding one equivalent of N2 and reducing the putative diazidotriazeneylnitrene species by two electrons, which rearranges to N-(1′H-1,5′-bitetrazol]-5-yl)methanediiminate (biTzI2−) dianionic ligand, which ligates the metal and dimerizes, and is isolated from pyridine as M(biTzI)]2Py6 (M = Mn, Fe, Zn, Cu, Ni). Reagent scope, product analysis, and quantum chemical calculations were combined to elucidate the mechanism of formation as a two-electron reduction preceding ligand rearrangement.Cyanuric triazide reacts with transition metal precursors, extruding N2 and reducing the ligand by two electrons, which breaks an aromatic ring and rearranges to a bitetrazolylmethanediiminate (biTzI2−) ligand, forming two new aromatic rings. |
| |
| Keywords: | |
|
|
