Nickel(II) complexes with N-(thio)phosphorylthioureas AdNHC(S)NHP(X)(OiPr)2: Versatile coordination of phosphoryl (XÂ =Â O) and thiophosphoryl (XÂ =Â S) derivatives

The reaction of the potassium salts of N-(thio)phosphorylated thioureas of the common formula AdN(H)C(S)N(H)P(X)(OiPr)2 (X = O, HLI; X = S, HLII) with the Ni(II) cation in aqueous EtOH leads to [Ni(LI,II)2] chelate complexes. The molecular structures of the thioureas HLI,II and the complexes [Ni(LI-N,S)2] and [Ni(LII-S,S′)2] were elucidated by single crystal X-ray diffraction analysis, IR, 1H and 31P NMR spectroscopy and microanalysis. In the complex [Ni(LI)2], the metal center is found to be in a square-planar N2S2 environment formed by the CS sulfur atoms and the P-N nitrogen atoms of two deprotonated LI ligands. The ligands are in a trans configuration. The Ni(II) atom in complex [Ni(LII)2], with the deprotonated thiourea LII, is coordinated in a square-planar fashion by the CS and PS sulfur atoms of two anionic ligands. The ligands are in a cis configuration.