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An excess of lithium or sodium in diethyl ether consistently reduces 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) to the mono-, di-, tri-and tetraanion, (dppbian)The process of reduction is easily observed by the change in colour of the solution, on going from the neutral ligand (yellow) to the monoanion (red), the dianion (green for Na or Li in Et 2 O; dark blue, followed by green, for Li in TMEDA), the trianion (brown) and the tetraanion (red-brown). In each reduction the maximum of the absorption, caused by electron transition from the HOMO of the respective form (dpp-bian)n− (n = 1−4), is shifted to the long-wavelength region in comparison to the previously reduced state. The disproportionation reactions (dpp-bian) 1− Ǟ (dpp-bian) 0 + (dpp-bian) 2− and (dpp-bian) 2−

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The reduction of 6,12-dichloro-1,2,3,4,7,8,9,10-octahydro-6H,12H-[1,2,3]benzodiazaphospholo[2,1-a][1,2,3]benzodiazaphosphole (3) by metallic magnesium in tetrahydrofuran (THF) affords the N,N'-fused bisphosphole 1 in 92% yield. The compound reveals a novel type of 10π-electron heteroaromatic system [NICS(0) = -11.4], containing a two-coordinate and formally divalent phosphorus atom. Compound 1 possesses a much higher coordination activity than many other diazaphospholes. This is caused by a novel type of complexation to a metal ion wherein the lone phosphorus pairs are not involved in metal coordination. Instead, the 10π-electron heteroaromatic system provides two electrons for P → M bond formation. Polarization of the ligand results in the formation of extended molecular associates or cluster compounds. Complexes of 1 with mercury dichloride [{(1)3HgCl}2(μ6-Cl)](+)Cl(-) (7) and tin dichlorides [1·SnCl2(PhMe solvate)] (8a) and [1·SnCl2] (8b) are, in fact, supramolecular in nature, containing multiple intermolecular short contacts. Crystals of complex 8a containing short Sn···Sn packing interactions were converted reversibly to metallic tin after workup with THF. The simple mixing of 1 and 3 (1:1) gave a P-P bridging dimeric species prone to easy dissociation. The addition of GeCl2(diox) to the equimolar mixture of 1 and 3 shifted the equilibrium to the formation of a poorly soluble salt-like dimer 6, which is, in fact, a stacked 18π-electron dication having a through-space delocalization of π electrons.

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