220917-07-7Relevant academic research and scientific papers
Polynuclear gold complexes with bridging selenido ligands. Theoretical studies of gold-gold interactions
Canales, Silvia,Mendizabal, Fernando
, p. 4985 - 4994 (2000)
The compounds [Se(AuPPh3)2] and [Se(Au2dppf)] are good precursors for the synthesis of highly aurated selenium-centered derivatives. Thus the reaction of [Se(AuPPh3)2] with various molar ratios of [Au(OTf)PPh3] affords the homoleptic species [Se(AuPPh3)n](OTf)n-2 (n = 3-6). Similarly, the treatment of [Se(Au2dppf)] with various stoichiometric ratios of [Au2(OTf)2(μ-dppf)] gives the polynuclear derivatives [(Au2dppf){Se(Au2dppf)}2](OTf)2, [Se(Au2dppf)2](OTf)2, and [Se(Au2dppf)3](OTf4. The compounds [Au{Se(AuPPh3)2}2]ClO4 and [Au{Se(Au2dppf)}2]ClO4 have been obtained by reaction of the precursors with [Au(tht)2]-ClO4 in a molar ratio of 2:1. Some of these derivatives have been characterized by X-ray diffraction studies and show unusual geometries, associated with gold-gold interactions. The latter have been studied theoretically using [Se(AuPH3)n](n-2)+ (n = 2-6) models at the HF and MP2 levels with quasi-relativistic pseudopotentials. There is a good agreement between experimental and theoretical geometries.
Coordination chemistry of gold catalysts in solution: A detailed NMR study
Zhdanko, Alexander,Stroebele, Markus,Maier, Martin E.
, p. 14732 - 14744 (2013/01/15)
Coordination chemistry of gold catalysts bearing eight different ligands [L=PPh3, JohnPhos (L2), Xphos (L3), DTBP, IMes, IPr, dppf, S-tolBINAP (L8)] has been studied by NMR spectroscopy in solution at room temperature. Cationic or neutral mononuclear complexes LAuX (L=L2, L3, IMes, IPr; X=charged or neutral ligand) underwent simple ligand exchange without giving any higher coordinate complexes. For L2AuX the following ligand strength series was determined: MeOHahex-3-yne -aMe 2S3CO2 -≈DMAP3-≈Cl -. Some heteroligand complexes DTBPAuX exist in solution in equilibrium with the corresponding symmetrical species. Binuclear complexes dppf(AuOTf)2 and S-tolBINAP(AuOTf)2 showed different behavior in exchange reactions with ligands depending on the ligand strength. Thus, PPh3 causes abstraction of one gold atom to give mononuclear complexes LLAuPPh3+ and (Ph3P) nAu+, but other N and S ligands give ordinary dicationic species LL(AuNu)22+. In reactions with different bases, LAu+ provided new oxonium ions whose chemistry was also studied: (DTBPAu)3O+, (L2Au)2OH+, (L2Au) 3O+, (L3Au)2OH+, and (IMesAu) 2OH+. Ultimately, formation of gold hydroxide LAuOH (L=L2, L3, IMes) was studied. Ligand- or base-assisted interconversions between (L2Au)2OH+, (L2Au)3O+, and L2AuOH are described. Reactions of dppf(AuOTf)2 and S-tolBINAP(AuOTf) 2 with bases provided more interesting oxonium ions, whose molecular composition was found to be [dppf(Au)2]3O2 2+, L8(Au)2OH+, and [L8(Au)2] 3O22+, but their exact structure was not established. Several reactions between different oxonium species were conducted to observe mixed heteroligand oxonium species. Reaction of L2AuNCMe+ with S2- was studied; several new complexes with sulfide are described. For many reversible reactions the corresponding equilibrium constants were determined. Copyright
