Transition-metal-mediated reduction and reversible double-cyclization of cyanuric triazide to an asymmetric bitetrazolate involving cleavage of the six-membered aromatic ring

Shivaiah Vaddypally; Vitaly G. Kiselev; Alex N. Byrne; C. Franklin Goldsmith; Michael J. Zdilla

doi:10.1039/D0SC04949B

Transition-metal-mediated reduction and reversible double-cyclization of cyanuric triazide to an asymmetric bitetrazolate involving cleavage of the six-membered aromatic ring†

Shivaiah Vaddypally,

^a Vitaly G. Kiselev,

^bcde Alex N. Byrne,^a C. Franklin Goldsmith

*^b and Michael J. Zdilla

*^a

Author affiliations

* Corresponding authors

^a Temple University, 1901 N. 13th St., Philadelphia, PA 19122, USA
E-mail: mzdilla@temple.edu

^b School of Engineering, Brown University, 184 Hope St., Providence, RI 02912, USA
E-mail: franklin_goldsmith@brown.edu

^c Novosibirsk State University, 1 Pirogova Str., 630090 Novosibirsk, Russia

^d Institute of Chemical Kinetics and Combustion SB RAS, 3 Institutskaya Str., 630090 Novosibirsk, Russia

^e 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.

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DOI: https://doi.org/10.1039/D0SC04949B
Article type: Edge Article
Submitted: 07 Sep 2020
Accepted: 01 Dec 2020
First published: 08 Dec 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry

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Chem. Sci., 2021,12, 2268-2275

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Transition-metal-mediated reduction and reversible double-cyclization of cyanuric triazide to an asymmetric bitetrazolate involving cleavage of the six-membered aromatic ring

S. Vaddypally, V. G. Kiselev, A. N. Byrne, C. F. Goldsmith and M. J. Zdilla, Chem. Sci., 2021, 12, 2268 DOI: 10.1039/D0SC04949B

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Chemical Science

Transition-metal-mediated reduction and reversible double-cyclization of cyanuric triazide to an asymmetric bitetrazolate involving cleavage of the six-membered aromatic ring†

Abstract

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Transition-metal-mediated reduction and reversible double-cyclization of cyanuric triazide to an asymmetric bitetrazolate involving cleavage of the six-membered aromatic ring

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