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

Abstract

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.

Metal-Free Reversible Double Cyclization of Cyanuric Diazide to an Asymmetric Bitetrazolate via Cleavage of the Six-Membered Aromatic Ring

“…In this reaction, the metal acts as a template to assemble the resulting bidentate biTzI ligand (Scheme 1B). 41 This report also showed that protonation of this ligand with an acid resulted in a reversion to 2-amino-4,6diazido-1,3,5-triazine (1), with rupture of the two fivemembered azole rings and re-formation of the six-membered aromatic ring (Scheme 1C). This reaction was also reversible; the addition of bis(trimethylsilyl)amidomanganese(II) (Scheme 1D; M = Mn) results in deprotonation of 1 by the amide ligands and reassembly of the bitetrazole around the manganese center.…”

“…A cycloaddition reaction of azide occurs on o -azidoazines (Scheme A), a reversible isomerization to a indole-like fused bicycle containing a tetrazole ring fused to the six-membered azine. ,,− We have recently reported a metal-based analogue of this reaction where the reduction of cyanuric triazide to an imide with the extrusion of N 2 resulted in subsequent rearrangement of the diazidocyanuric imide into the dianionic (1,5′-bitetrazolyl)methanediiminate (biTzI 2– ) ligand, an asymmetrically linked bitetrazole, formed via cleavage of the aromatic C–N bond, followed by cyclization of the two remaining azides. In this reaction, the metal acts as a template to assemble the resulting bidentate biTzI ligand (Scheme B) . This report also showed that protonation of this ligand with an acid resulted in a reversion to 2-amino-4,6-diazido-1,3,5-triazine ( 1 ), with rupture of the two five-membered azole rings and re-formation of the six-membered aromatic ring (Scheme C).…”

Energetic coordination compounds: self-assembled from the nitrogen-rich energetic C–C bonded pyrazoles and triazoles

“…In recent years, the development of high-energy density materials (HEDMs) based on nitrogen, oxygen-rich heterocyclic energetic ligands with metal complexes and associated coordination polymers have garnered significant interest for military and civilian applications. 1,2 Compared with conventional energetic organic molecules, energetic coordination compounds (ECCs) have several noteworthy advantages, including high density, heats of formation and superior thermal decomposition temperature with great hardness and strength. 3–5 Considering their unique structural features and physicochemical characteristics, ECCs have received significant attention from researchers in the energetic materials domain.…”

Spirooxazine-Based Dual-Sensing Probe for Colorimetric Detection of Cu2+ and Fe3+ and Its Application in Drinking Water and Rice Quality Monitoring

“… 32 − 36 Moreover, their sensing mechanism in response to metal ions was also proposed based on the metal–ligand coordination and chemical reactions, such as bond cleavage, bond formation, rearrangement, and cyclization. 37 To date, several chemosensors as colorimetric probes with high selectivity and sensitivity as a facile and rapid tool for on-site analysis of metal ions have been reported. 38 − 42 …”

“…This subsequently leads to a spectral change in their signals and sometimes a structural change can be observed in some chemosensors . Several organic molecules, for example, rhodamine, anthracene, benzothiadiazole, squaraine, and phenothiazine, have been studied as potential chemosensors to detect a wide range of metal ions. − Moreover, their sensing mechanism in response to metal ions was also proposed based on the metal–ligand coordination and chemical reactions, such as bond cleavage, bond formation, rearrangement, and cyclization . To date, several chemosensors as colorimetric probes with high selectivity and sensitivity as a facile and rapid tool for on-site analysis of metal ions have been reported. − …”