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One-electron oxidation of the non-innocent 1,2,4-diazaphospholide anion [3,5-R2dp]-(R = Cy(1),iPr(2),or Ph(3)) by AsCl3 generated a diagonal paddlewheel diarsine [L2(As-As)L2](L = η1,η1-3,5-R2dp,R = Cy(4),with very short As-As single bond lengths 2.45(A).