Syntheses and Structures of Dinuclear Gold(I) Dithiophosphonate Complexes and the Reaction of the Dithiophosphonate Complexes with Phosphines: Diverse Coordination Types
详细信息 查看全文
- 作者：Angelo Maspero ; Ibrahim Kani ; Ahmed A. Mohamed ; Mohammad A. Omary ; Richard J. Staples ; and John P. Fackler ; Jr.
- 刊名：Inorganic Chemistry
- 出版年：2003
- 出版时间：August 25, 2003
- 年：2003
- 卷：42
- 期：17
- 页码：5311 - 5319
- 全文大小：219K
- 年卷期：v.42,no.17(August 25, 2003)
- ISSN：1520-510X
文摘
The dinuclear gold(I) dithiophosphonate complex, [Au2(dtp)2] (1), where dtp = [S2P(R)(OR')]- with R = p-C6H4OCH3; R'= c-C5H9, has been synthesized and its reaction studied with the phosphine ligands PPh3 and Ph2P(CH2)nPPh2 (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, thedinuclear open-ring complexes Au2(dppm)(dtp)2 (2), Au2(dppe)(dtp)2 (3), Au2(dppp)(dtp)2 (4), Au2(dppb)(dtp)2 (5)were formed (dppm = diphenylphosphinomethane; dppe = diphenylphosphinoethane; dppp = diphenylphosphinopropane; dppb = diphenylphosphinobutane). The reaction with dppm is stoichiometry-dependent. Thus, when 1reacts with 2 equiv of dppm, the ionic complex [Au2(dppm)2(dtp)]dtp forms. This dtp counterion was exchangedwith tetrafluoroborate to yield [Au2(dppm)2(dtp)]BF4, the crystallization of which afforded two interconvertible isomers,6-yellow and 7-white. Reaction of 1 with PPh3 affords the tetracoordinate mononuclear complex [Au(dtp)(PPh3)2](8). The molecular structures of 1-8 were confirmed by X-ray crystallography and show multiple coordinationmodes and geometries. The crystal structures of 1 and its reaction products with dppm (2, 6, 7) show shortintramolecular Au···Au aurophilic bonding interactions of 2.95-3.10 Å while no intermolecular interactions werediscernible. However, reaction products of 1 with longer-chain Ph2P(CH2)nPPh2 ligands, n = 2-4, exhibit structuresthat lack both intra- and intermolecular Au···Au interactions.