Deprotonation of a hydrophosphorane and synthesis of the Ni(II) metallophosphorane [NiCl{P(OC6H4N(CH3))2}(P(CH3)3)2]

The hydrophosphorane [HP(OC6H4N(CH3))(2)] has been deprotonated using lithium tetramethylpiperidide to produce Li[P(OC6H4N(CH3))(2)] (1). Compound 1 reacts further with NiCl2(PMe3)(2) to form the Ni(II) phosphoranide complex [NiCl{P(OC6H4N(CH3))(2)}(P(CH3)(3))(2)] (2). The crystal structures of both 1 and 2 were determined. The structure of 1 is dimeric with bridging lithium cations and also features one THF solvent molecule coordinated to each lithium cation; the geometry about the lithium atom is tetrahedral. The structure of 2 displays tetrahedral distortion from an idealized square-planar geometry. Both 1 and 2 characterized by H-1 and P-31 NMR, with C-13 NMR for 2 also. DFT calculations (B3LYP/6311++G(2df,2p)) were also done on 2; both the NMR and DFT studies indicate p-donation from the metal to the pentacoordinate phosphorus. (C) 2014 Elsevier B.V. All rights reserved.