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. 2017 Nov 6;56(21):12678-12681.
doi: 10.1021/acs.inorgchem.7b01902.

Direct Evidence for Neutral N-Pyrazolyl Radicals: Paddlewheel Dibismuthanes Bearing Pyrazolato Ligands with Very Short Bi-Bi Single Bonds

Ming-Gang Zhao  1 , Ting-Ting Hao  1 , Xiang Zhang  1 , Jian-Ping Ma  2 , Ji-Hu Su  3 , Wenjun Zheng  1   4
Affiliations

Direct Evidence for Neutral N-Pyrazolyl Radicals: Paddlewheel Dibismuthanes Bearing Pyrazolato Ligands with Very Short Bi-Bi Single Bonds

Ming-Gang Zhao et al. Inorg Chem. .

Abstract

Neutral N-pyrazolyl radicals [3,5-R2pz]• as reactive intermediates were generated by one-electron oxidization of the corresponding 3,5-disubstituted pyrazolato anions [3,5-R2pz]- (R = tBu, Ph) with BiCl3 and trapped by the use of 5,5-dimethyl-1-pyrroline-N-oxide as a spin trap, which was confirmed by electron paramagnetic resonance spectral analysis. With dimerization of the postulated pyrazolato low-valent BiII radical species, two novel paddlewheel pyrazolatodibismuthanes [L2(Bi-Bi)L2] [L = η1,η1-3,5-R2pz; R = tBu (5α, 5β, and 5γ), Ph (6)] were isolated and structurally characterized.

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