The compound [CoII{HN(OPPh2)(SPPh2)‐O}2I2] (1) was synthesised by the reaction of cobalt in powder with the iodine adduct of tetraphenylthiooxoimidodiphosphinic acid, HN(OPPh2)(SPPh2), in Et2O; treatment of compound 1 with NaOH resulted in deprotonation of the ligands bound to the metal ion and a separation of [CoII{N(OPPh2)(SPPh2)‐O,S}2] (2). Molecular structures of complexes 1 and 2 were elucidated by X‐ray diffraction analysis, which revealed a CoI2O2 tetrahedral core for compound 1 in which two neutral ligands bind through the oxygen atoms the CoII ion, and a tetrahedral CoO2S2 core for compound 2 with the oxygen and sulfur atoms of each anionic ligand chelating a CoII centre. Variable‐temperature magnetic susceptibility measurements are consistent with tetrahedral high‐spin (S = 3/2) CoII that possesses a 4A2 ground state with best fit parameters g = 2.25, |D| = 12.0 cm–1 and g = 2.37, |D| = 11.9 cm–1 for complexes 1 and 2, respectively. The compounds were further characterised by UV/Vis and IR spectroscopy. DFT calculations were performed on model complexes [CoII{N(OPH2)(SPH2)‐O,S}2] (3) and [CoII{N(SPH2)2‐S,S′}2] (4) to compare the electronic properties of the CoO2S2 and CoS4 cores. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

The reaction of gold powder with the iodine adduct of Ph2P(S)NHP(S)Ph2 (HL) in Et2O gave the complex [Au(L)I2] under mild reaction conditions. Its crystal structure is comprised of discrete, monomeric molecules with a central AuIII ion bonded to two sulfur atoms by an anionic ligand L and two iodide anions in a slightly distorted square‐planar coordination geometry. From the reaction of [AuCl3(tht)] with HL in CH2Cl2 it is possible, besides the main complex [Au(L)]2, to separate the neutral AuI complex [Au(L′2H)], L′ = [Ph2P(S)NP(O)Ph2]−, the crystal structure of which features a AuI ion linearly coordinated to two sulfur atoms and a proton bridging two oxygen atoms of the PO groups. 31P NMR CP MAS spectroscopy is in accordance with the nature of the ligands in the complex. The reaction chemistry of [Au(L′2H)] in CH2Cl2 towards the acid CF3COOH and the organic base 1,8‐bis(dimethylamino)naphthalene is reported. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

The copper(I) compounds [Cu + is a possible structural model compound for the metal site in Ace1 and Mac1 transcription factors. In compound 2, two neutral HL ligands bind a Cu I ion in an S,SЈ-isobidentate chelating fashion to

The complex [Hg(HL)I2] (1) has been synthesised by reacting liquid Hg(0) in Et2O under mild reaction conditions with the I2 adduct of HL, HL·I2, while HgL2 (2) has been obtained from the reaction of compound 1 with HL in CH3CN. A single‐crystal X‐ray investigation of 1 shows four independent molecules in the asymmetric unit, each of which contains an HgII ion coordinated to two iodine atoms and two sulfur atoms of one bidentate neutral ligand in a distorted tetrahedral coordination geometry. Compound 2 consists of two anionic ligands coordinated to an HgII ion, which again displays a distorted tetrahedral coordination sphere. The reaction of 2 with HI (55 wt.‐% in water) affords [Hg(HL)2](I)2 (3). Compounds 1, 2, and 3 have been characterised by FT‐IR and 31P NMR spectroscopy. Density functional calculations suggest that compound 3 should feature a distorted tetrahedral coordination around the metal centre, with unequal Hg−S bond lengths. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)