122092-52-8Relevant articles and documents
1,1'-Bis(diphenylphosphino)ferrocene complexes of gold(I). Polymeric n and dimeric (NO3)2
Phang, Lai-Tee,Hor, T. S. Andy,Zhou, Zhong-Yuan,Mak, Thomas C. W.
, p. 253 - 261 (1994)
Addition of molar equivalent of to (dppf) gives an intermediate complex x (1) which readily polymerises in solution to give n*nCH2Cl2 (2).X-ray diffraction analysis of 2 revealed a repeating unit of propagating one-dimensionally along the c axis to give a zigzag chain.Complex 1 methathesises with AgNO3 to give x which reacts with HCO2Na to give (NO3)2*2H2O (3) as one of the products.The X-ray structure of 3 shows a centrosymmetric dimeric framework with two chelates bridged by a dppf ligand.Both 2 and 3 show negligible inter- or intramolecular Au...Au interactions.Key words: Gold; Iron; Ferrocene; Diphosphine; Phosphine; Polymer
Synthesis and solution properties of the boron-containing clusters HM4(CO)12BAu2(dppf) (M=Fe or Ru) and the competitive formation of 2(dppf) for M=Ru (dppf=1,1'-bis(diphenylphosphino)ferrocene). Molecular structure of HRu4(CO)12BAu2(dppf)*2CHCl3
Draper, Sylvia M.,Housecroft, Catherine E.,Rheingold, Arnold L.
, p. 9 - 20 (1992)
The reaction of (M=Fe or Ru) with ClAu(dppf)AuCl (dppf=1,1'-bis(diphenylphosphino)ferrocene) leads to HM4(CO)12BAu2(dppf) in which the environment of the boron atom depends upon the identity of M.For M=Ru, the boron atom is interstitial, with the hydride ligand wholly associated with the tetraruthenium framework.For M=Fe, an isomer equilibrium exists in solution between a metallaborane and a metallaboride cluster with the former, Fe4(CO)12BHAu2(dppf) (1) being the dominant species.The difference in structure is attributed to the increase in size of the tetrametal butterfly framework from Fe4 to Ru4 and follows the pattern previously noted for HM4(CO)12BAu2(PPh3)2.For M=Ru, the formation of HRu4(CO)12BAu2(dppf) (3) competes with that of the linked bicluster 2(dppf) (2).A crystallographic structural determination of 3 has revealed that the hexametal skeleton in 3 encapsulates the boron atom but is non-octahedral.The two Au atoms are related by a molecular C2 axis and each bridges one B-Ruwingtip edge.The orientation of the ferrocenyl group with respect to the cluster core is controlled by the location of the gold atoms and the two C5 rings are locked in an approximately mutually eclipsed position.In solution, 1H NMR spectroscopy in the Cp region has been used to study the fluxional behaviour of 3; three processes are mutually dependent (i) a rocking motion of the two Au atoms with respect to the Ru4B core (ii) inversion at the phosphorus atoms (iii) cyclopentadienyl ring twisting.
An efficient approach to chloro(organophosphine) gold(i) complexes for the synthesis of auranofin
Wang, Junchang,Mi, Xuemeng,Wang, Jiazhe,Yang, You
, p. 634 - 637 (2017)
A practical and efficient synthesis of chloro(organophosphine) gold(i) complexes is reported. Employment of 4,4′-dihydroxydiphenyl sulfide as a safe and non-irritating reductant is highlighted for the generation of Au(i)-S intermediates, which could be trapped by mono- and bidentate phosphine ligands to provide organophosphine gold(i) complexes. The utility of the present method is further demonstrated by the synthesis of the antiarthritic drug auranofin.
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
