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1,2,4-Triazolato paddlewheel dibismuth complexes with very short Bi(ii)–Bi(ii) bonds: bismuth(iii) oxidation of 1,2,4-triazolato anions into neutral N-1,2,4-triazolyl radicals

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Abstract

Bismuth(III) oxidation of 3,5-di-substituted-1,2,4-triazolato anions afforded a paddlewheel 1,2,4-triazolato dibismuth complex [L2(Bi–Bi)L2] (L = η11-3,5-R2tz, R = Ph (3), iPr (4)) with very short Bi(II)–Bi(II) bonds (2.8650(4)−2.8721(3) Å). The reaction involved the intermediates of the organobismuth radical [Bi(R2tz)2]˙ and neutral N-1,2,4-triazolyl radical [3,5-R2tz]˙. The dimerization of the former produced the corresponding dibismuth complex while the latter was trapped by using spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) to give the radical adduct of {(3,5-R2tz)(DMPO)}˙ which was unambiguously evidenced by EPR analysis.

Graphical abstract: 1,2,4-Triazolato paddlewheel dibismuth complexes with very short Bi(ii)–Bi(ii) bonds: bismuth(iii) oxidation of 1,2,4-triazolato anions into neutral N-1,2,4-triazolyl radicals

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Article information


Submitted
16 Sep 2020
Accepted
09 Oct 2020
First published
09 Oct 2020

Dalton Trans., 2020, Advance Article
Article type
Communication

1,2,4-Triazolato paddlewheel dibismuth complexes with very short Bi(II)–Bi(II) bonds: bismuth(III) oxidation of 1,2,4-triazolato anions into neutral N-1,2,4-triazolyl radicals

M. Zhao, L. Li, R. He, X. Zhang, J. Ma, J. Su and W. Zheng, Dalton Trans., 2020, Advance Article , DOI: 10.1039/D0DT03225E

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