61359-40-8Relevant articles and documents
Alkyne/alkene/allene-induced disproportionation of cationic gold(i) catalyst
Kumar, Manish,Jasinski, Jacek,Hammond, Gerald B.,Xu, Bo
supporting information, p. 3113 - 3119 (2014/03/21)
The first detailed experimental study of the deactivation of cationic gold was conducted, and the influence of each component in the reaction system (substrate, counterion, solvent) on the decay process was examined. It was found that a substrate (alkyne/allene/alkene)-induced disproportionation of gold(I) may play a key role in the decay process. Our mechanism is supported by kinetic, XPS, voltammetry studies, and high-resolution ESI-MS data. The first detailed experimental study of the deactivation of cationic gold was conducted, and the influence of each component in the reaction system (substrate, counterion, solvent) on the decay process was examined. It was found that a substrate (alkyne/allene/alkene)-induced disproportionation of gold(I) may play a key role in the decay process (see scheme; TFa=atrifluoromethanesulfonyl).
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
Group 11 complexes with unsymmetrical P,S and P,Se disubstituted ferrocene ligands
Aguado, Javier E.,Silvia Canales,Gimeno, Concepcion,Jones, Peter G.,Laguna, Antonio,Dolores Villacampa
, p. 3005 - 3015 (2007/10/03)
The reaction of the unsymmetrical ligands l-diphenylphosphino-1′-(phenylsulfanyl)ferrocene and 1-diphenylphosphino-1′-(phenylselenyl)ferrocene, Fc(EPh)PPh2 (E = S, Se), with several group 11 metal derivatives leads to the synthesis of complexes of the type [MX{Fc(EPh)PPh2}] (M = Au, X = Cl, C 6F5; M = Ag, X = OTf), (OTf = trifluoromethanesulfonate), [M{Fc(EPh)PPh2}2]X (M = Au, X = ClO4; M = Ag, X = OTf), [M(PPh3){Fc(EPh)PPh2}]OTf (M = Au, Ag), [Au 2{Fc(SPh)PPh2}2](ClO4)2, [Au(C6F5)2{Fc(SePh)PPh2}]ClO 4, [Au(C6F5)3{Fc(EPh)PPh 2}], [Au2(C6F5) 6{Fc(SePh)PPh2}] or [Cu{Fc(EPh)PPh2} 2]PF6 (E = S, Se). In these complexes coordination depends upon the metal centre; with gold it takes place predominantly to the phosphorus atom and with silver and copper to both phosphorus and chalcogen atoms. The treatment of some of the gold complexes with other metal centres affords heterometallic derivatives that in some cases are in equilibrium with the homometallic derivatives. Several compounds have been characterized by X-ray diffraction, four pairs of homologous compounds, yet not a single pair is isotypic. In many of them a three dimensional network is formed through secondary bonds such as hydrogen bonds, Au ... Cl or Au ... Se interactions. The complex [Ag(OTf){Fc(SePh)PPh2}] forms one-dimensional chains through trifluoromethanesulfonate bridging ligands. The Royal Society of Chemistry 2005.
