Access to 1,2,3-triphospholide ligands by reduction of di-tert-butyldiphosphatetrahedrane.

Di-tert-butyldiphosphatetrahedrane (tBuCP)2 (A) is a reactive tetrahedral molecule which may serve as a source of new phosphaorganic molecules and ligands. However, the redox chemistry of this compound has not yet been investigated. Here, we show that the reduction of A with alkali metals (AM = Li, Na, K, Rb and Cs) affords 1,2,3-triphospholides [AM(crown ether)][1,2,3-P3C2tBu2] (1-5, [AM(crown ether)] = [Li([12]crown-4)2]+, [Na([15]crown-5)2]+, [K([18]crown-6)]+, [Rb([18]crown-6)]+, and Cs+) with 1,3-diphospholides [AM(crown ether)][1,3-P2C3tBu3] (6-10) formed as by-products. The potassium salt 3 was isolated on a preparative scale, allowing for reactivity studies. Transmetalation with iron(II) and ruthenium(II) chlorides yielded the sandwich complexes [Cp*M(η5-1,2,3-P3C2tBu2)] (11, M = Fe; 12, M = Ru, Cp* = C5Me5) featuring η5-coordinated triphospholide ligands. Treatment of 3 with [Cp2Fe][BAr4F] or [H(Et2O)2BAr4F] (BAr4F = B{C6H3(CF3)2}4) afforded the polyphosphorus compound tBu4C4P6 (13), which presumably results from the dimerisation of a 1,2,3-triphospholyl radical intermediate (1,2,3-P3C2tBu2)˙ (3˙). Tetracyclic 13 is closely structurally related to an isomer of the hydrocarbon hypostrophene (C10H10).