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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Transition-metal-mediated reduction and reversible double-cyclization of cyanuric triazide to an asymmetric bitetrazolate involving cleavage of the six-membered aromatic ring. / Vaddypally, Shivaiah; Kiselev, Vitaly G.; Byrne, Alex N. et al.

In: Chemical Science, Vol. 12, No. 6, 08.12.2020, p. 2268-2275.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{f5161e64dfb24fc2938a033d31ef2248,

title = "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 several transition metal precursors, extruding one equivalent of N2and reducing the putative diazidotriazeneylnitrene species by two electrons, which rearranges toN-(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.",

author = "Shivaiah Vaddypally and Kiselev, {Vitaly G.} and Byrne, {Alex N.} and Goldsmith, {C. Franklin} and Zdilla, {Michael J.}",

note = "Funding Information: M. J. Z. and C. F. G. gratefully acknowledge nancial support from ONR (N00014-19-1-2087 and N00014-1-61-2054). V. G. K. acknowledges the Supercomputer Center of Novosibirsk State University and the Russian Science Foundation for a nancial support of the computational part of this work (project 19-73-20217). S. V. and M. J. Z. are supported by the National Science Foundation under award 1800105. This work was also supported by Brown University through the use of the facilities of its Center for Computation and Visualization. The authors thank Prof. Steven A. Fleming for helpful conversations surrounding cycloaddition mechanisms, and Charles Debrosse for helpful conversations concerning NMR assignments. Finally, the authors thank Prof. Edward G. Gillon of the University of Iowa for helpful conversations on the preparation and handling of cyanuric triazide. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2021. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.",

year = "2020",

month = dec,

day = "8",

doi = "10.1039/d0sc04949b",

language = "English",

volume = "12",

pages = "2268--2275",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "6",

}

RIS

TY - JOUR

T1 - Transition-metal-mediated reduction and reversible double-cyclization of cyanuric triazide to an asymmetric bitetrazolate involving cleavage of the six-membered aromatic ring

AU - Vaddypally, Shivaiah

AU - Kiselev, Vitaly G.

AU - Byrne, Alex N.

AU - Goldsmith, C. Franklin

AU - Zdilla, Michael J.

N1 - Funding Information: M. J. Z. and C. F. G. gratefully acknowledge nancial support from ONR (N00014-19-1-2087 and N00014-1-61-2054). V. G. K. acknowledges the Supercomputer Center of Novosibirsk State University and the Russian Science Foundation for a nancial support of the computational part of this work (project 19-73-20217). S. V. and M. J. Z. are supported by the National Science Foundation under award 1800105. This work was also supported by Brown University through the use of the facilities of its Center for Computation and Visualization. The authors thank Prof. Steven A. Fleming for helpful conversations surrounding cycloaddition mechanisms, and Charles Debrosse for helpful conversations concerning NMR assignments. Finally, the authors thank Prof. Edward G. Gillon of the University of Iowa for helpful conversations on the preparation and handling of cyanuric triazide. Publisher Copyright: © The Royal Society of Chemistry 2021. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2020/12/8

Y1 - 2020/12/8

N2 - Cyanuric triazide reacts with several transition metal precursors, extruding one equivalent of N2and reducing the putative diazidotriazeneylnitrene species by two electrons, which rearranges toN-(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.

AB - Cyanuric triazide reacts with several transition metal precursors, extruding one equivalent of N2and reducing the putative diazidotriazeneylnitrene species by two electrons, which rearranges toN-(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.

UR - http://www.scopus.com/inward/record.url?scp=85101160284&partnerID=8YFLogxK

U2 - 10.1039/d0sc04949b

DO - 10.1039/d0sc04949b

M3 - Article

C2 - 34163993

AN - SCOPUS:85101160284

VL - 12

SP - 2268

EP - 2275

JO - Chemical Science

JF - Chemical Science

SN - 2041-6520

IS - 6

ER -

ID: 27967635