| 12924903 |
Maspero A, Kani I, Mohamed AA, Omary MA, Staples RJ, Fackler JP Jr: Syntheses and structures of dinuclear gold (I) dithiophosphonate complexes and the reaction of the dithiophosphonate complexes with phosphines: diverse coordination types. Inorg Chem. 2003 Aug 25;42(17):5311-9.
The dinuclear gold (I) dithiophosphonate complex, [Au (2)(dtp)(2)] (1), where dtp = [S (2) P (R)(OR')](-) with R = p-C (6) H (4) OCH (3); R'= c-C (5) H (9), has been synthesized and its reaction studied with the phosphine ligands PPh (3) and Ph (2) P (CH (2))(n) PPh (2) (n = 1-4). Compound 1 contains two gold atoms homobridged by the anionic dithiophosphonate ligand, forming an eight-membered ring complex in a chair form. After the reaction of 1 with diphosphine ligands, the dinuclear open-ring complexes Au (2)(dppm)(dtp)(2) (2), Au (2)(dppe)(dtp)(2) (3), Au (2)(dppp)(dtp)(2) (4), Au (2)(dppb)(dtp)(2) (5) were formed (dppm = diphenylphosphinomethane; dppe = diphenylphosphinoethane; dppp = diphenylphosphinopropane; dppb = diphenylphosphinobutane). The reaction with dppm is stoichiometry-dependent. Thus, when 1 reacts with 2 equiv of dppm, the ionic complex [Au (2)(dppm)(2)(dtp)] dtp forms. This dtp counterion was exchanged with tetrafluoroborate to yield [Au (2)(dppm)(2)(dtp)] BF (4), the crystallization of which afforded two interconvertible isomers, 6-yellow and 7-white. Reaction of 1 with PPh (3) affords the tetracoordinate mononuclear complex [Au (dtp)(PPh (3))(2)] (8). The molecular structures of 1-8 were confirmed by X-ray crystallography and show multiple coordination modes and geometries. The crystal structures of 1 and its reaction products with dppm (2, 6, 7) show short intramolecular Au.Au aurophilic bonding interactions of 2.95-3.10 A while no intermolecular interactions were discernible. However, reaction products of 1 with longer-chain Ph (2) P (CH (2))(n) PPh (2) ligands, n = 2-4, exhibit structures that lack both intra- and intermolecular Au.Au interactions. |
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