One-electron oxidation of the 1,2,4-diazaphospholide anion [3,5-R2dp](-) by BiCl3 generated several remarkable paddlewheel dibismuthanes [L2(Bi-Bi)L2] (L = η(1),η(1)-3,5-R2dp, R = tBu, iPr, or Ph) with very short Bi-Bi single bond lengths (2.7964(4)-2.8873(3) Å).

Neutral N-pyrazolyl radicals [3,5-Rpz] as reactive intermediates were generated by one-electron oxidization of the corresponding 3,5-disubstituted pyrazolato anions [3,5-Rpz] (R = tBu, Ph) with BiCl 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 Bi radical species, two novel paddlewheel pyrazolatodibismuthanes [L(Bi-Bi)L] [L = η,η-3,5-Rpz; R = tBu (5α, 5β, and 5γ), Ph (6)] were isolated and structurally characterized.

The regioselective N-addition/substitution reaction between α-alkylidene pyrazolinones and propargyl sulfonium salts has been developed to construct functionalized allylthio-containing pyrazolones with moderate to excellent yields. α-Alkylidene pyrazolinones act as N-nucleophilic agents which are distinguished from reported C-nucleophilic reactions. Excellent regioselectivity, readily available starting materials, the broad range of substrates, gram-scale synthesis, and simple operation illustrate the synthetic advantages of this new reaction pathway.

One-electron reduction of SbCl3 with the non-innocent 1,2,4-diazaphospholide anion [3,5-R2dp](-) produced straightforwardly three unprecedented paddlewheel distibines [L2(Sb-Sb)L2] (L = η(1),η(1)-3,5-R2dp, R = tBu (4), iPr (5α, 5β), or Cy (6)) with very short Sb-Sb bond lengths (2.6691(8)-2.7451(8) Å). The novel structures were rationalized by DFT calculations.

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