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One-electron oxidation of non-innocent 1,2,4-diazaphospholides [3,5-R2dp]–(R = tBu(1),iPr(2),Ph(3))with BiCl3 led to several rare paddlewheel dibismuthanes [L2(Bi-Bi)L2](L = η1,η1-3,5-R2dp,R = tBu(4),iPr(5α,5β),Ph(6))that have very short Bi–Bi single bond lengths in a range of 2.7964(4)–2.8873(3)(A)and the Bi–Bi bond lengths in 4 even shorter than Bi–Bi double bond distances in dibismuthenes.DFT computation suggested that the shorten Bi–Bi bond distances arise mainly from the “pulling closer” effect due to the positive bonding interaction between the fragment orbital of the 1,2,4-diazaphospholides and Bi–Bi σ bonding orbital as well as to the short N–N bonds of the η1,η1-bridged ligands.