The reaction of the 17e nickel(I) radical [CpNi(IDipp)] (1, IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with P4 results in a nickel tetraphosphide [{CpNi(IDipp)}2(μ-η(1):η(1)-P4)] with a butterfly-P4(2-) ligand; related chalcogenides [{CpNi(IDipp)}2(μ-E2)] (E = S, Se, Te) and [{CpNi(IDipp)}2(μ-E3)] (E = S, Se) are formed with S8, Se∞ and Te∞.
Although the chemistry of transition metal polyphosphide anions has attracted significant attention, there are few reports of studies in which such species have been synthesized directly from white phosphorus. [K(OEt ) {Co(BIAN)(cod)}] (1, BIAN=1,2-bis(2,6-diisopropylphenylimino)acenaphthene, cod=1,5-cyclooctadiene), which is readily prepared by ligand exchange from [K(thf) {Co(cod) }], reacts with P to afford [{K(thf)} {(BIAN)Co} (μ-η :η -P )] (2 a) in 61 % yield (isolated product). [{K(OEt )} {(BIAN)Co} (μ-η :η -P )] (2 b) and [K([18]crown-6)(MeCN)] [{(BIAN)Co} (μ-η :η -P )] (2 c) were obtained by recrystallizing 2 a from diethyl ether and acetonitrile (and using [18]crown-6 in case of 2 c). Oxidation of 2 a with [Cp Fe]BAr (one equivalent) and subsequent recrystallization of the product from different solvents gave [K(OEt ){(BIAN)Co} (μ-η :η -P )] (3 a) and [K(dme) ][{(BIAN)Co} (μ-η :η -P )] (3 b; dme=1,2-dimethoxyethane). Neutral [{(BIAN)Co} (μ-η :η -P )] (4) was obtained in moderate yield by oxidizing 2 a with two equivalents of [Cp Fe]BAr . The new complexes were characterized by NMR, EPR (in the case of 3 a), and UV/Vis spectroscopy, and elemental analysis. The molecular structures revealed by X-ray crystallography display planar cyclic or open-chain P units sandwiched between {(BIAN)Co} fragments.
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