- 1,1'-Bis(diphenylphosphino)ferrocene complexes of gold(I). Polymeric n and dimeric (NO3)2
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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
- Phang, Lai-Tee,Hor, T. S. Andy,Zhou, Zhong-Yuan,Mak, Thomas C. W.
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- Synthesis, structures and anti-malaria activity of some gold(i) phosphine complexes containing seleno- and thiosemicarbazonato ligands
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A series of both mono- and dinuclear gold(i) phosphine complexes containing monoanionic seleno- and thiosemicarbazones as ligands were prepared and fully characterized by spectroscopic methods and, in some cases, by single crystal X-ray diffraction. The in vitro anti-malaria activity of some of these compounds was investigated in chloroquine sensitive strains of Plasmodium falciparum. The IC50 results show that the sulfur containing compounds exhibit activity similar to that of chloroquine, whilst the selenium derivatives display only moderate anti-malaria activity.
- Molter, Anja,Rust, Joerg,Lehmann, Christian W.,Deepa, Ganesh,Chiba, Peter,Mohr, Fabian
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- 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
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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.
- Draper, Sylvia M.,Housecroft, Catherine E.,Rheingold, Arnold L.
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- Studies on gold(I) complexes of 1,1'-bis(diphenylphosphino)ferrocene
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The synthesis and 197Au, 57Fe Moessbauer and 31P NMR spectroscopic data for a series of Au1 complexes of 1,1'-bis(diphenylphosphino)ferrocene (fdpp) are reported.Two different Au1 coordination geometries are apparent in the solid state, linear and trigonal.There is no evidence in the solid state for a tetrahedral species +, but 31P NMR spectroscopy indicates its existence in solution.Chemical oxidation fo the complexes does not yield the expected ferrocenium derivatives.In accord with this, cyclic voltammetry reveals there to be no observable electrochemical processes in the timescales investigated (500-20 mV/s).
- Houlton, A.,Roberts, R.M.G.,Silver, J.,Parish, R.V.
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- An efficient approach to chloro(organophosphine) gold(i) complexes for the synthesis of auranofin
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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.
- Wang, Junchang,Mi, Xuemeng,Wang, Jiazhe,Yang, You
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- Auranofin and related heterometallic gold(I)-thiolates as potent inhibitors of methicillin-resistant Staphylococcus aureus bacterial strains
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A series of new heterometallic gold(I) thiolates containing ferrocenyl-phoshines were synthesized. Their antimicrobial properties were studied and compared to that of FDA-approved drug, auranofin (Ridaura), prescribed for the treatment of rheumatoid arthritis. MIC in the order of one digit micromolar were found for most of the compounds against Gram-positive bacteria Staphylococcus aureus and CA MRSA strains US300 and US400. Remarkably, auranofin inhibited S. aureus, US300 and US400 in the order of 150-300 nM. This is the first time that the potent inhibitory effect of auranofin on MRSA strains has been described. The effects of a selected heterometallic compound and auranofin were also studied in a non-tumorigenic human embryonic kidney cell line (HEK-293).
- Hokai, Yozane,Jurkowicz, Boruch,Fernández-Gallardo, Jacob,Zakirkhodjaev, Nuruddinkodja,Sanaú, Mercedes,Muth, Theodore R.,Contel, María
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- Synthesis and structural studies of some gold(I) complexes containing selenoureato ligands
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N,N-Diethyl-N′-4-nitrobenzoylselenourea (HLSe) reacts with the mono- and dinuclear phosphine gold(I) chloro complexes [AuCl(PR 3)] (R=Ph, o-tol, Et) and [Au2Cl2(μ-P-P)] (P-P=dppm, dppe, dppp, dppb, dppf) in the presence of base to give gold(I) phosphine selenoureato complexes [Au(LSe)(PR3)] [R=Ph (1), o-tol (2), Et (3)], [Au2(LSe)2(μ-P-P)] [P-P=dppm (4), dppe (5), dppp (6), dppb (7), dppf (8)] in excellent yields. The compounds were fully characterised by spectroscopic methods and, in the case of compounds 1, 5 and 8, by single crystal X-ray diffraction. The compounds consist of a gold atom bound in linear fashion to the phosphine ligand and the selenium atom from the deprotonated acylselenourea. These complexes thus represent the first examples of acylselenoureato metal compounds in which the ligands do not adopt the typical O,Se chelating mode but rather coordinate to the metal only through the selenium atom.
- Molter, Anja,Mohr, Fabian,Rust, Joerg,Lehmann, Christian W.
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p. 10586 - 10591,6
(2012/12/12)
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- Coordination chemistry of gold catalysts in solution: A detailed NMR study
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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
- Zhdanko, Alexander,Stroebele, Markus,Maier, Martin E.
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p. 14732 - 14744
(2013/01/15)
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- Synthesis, characterization and bromination of bis(phosphinoferrocenyl) gold(I) compounds
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Reaction of [(dppf)Au2Br2] (3) {dppf = 1,1′-bis(diphenylphosphino)ferrocene} and [(dippf)Au2Br2] (4) {dippf = 1,1′-bis(diisopropylphosphino)ferrocene} with excess bromine yields two new complexes [(C5
- Segapelo, Tebogo V.,Guzei, Ilia A.,Darkwa, James
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p. 701 - 708
(2008/04/05)
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- 1,1′-Bis(diphenylphosphino)ferrocene (dppf) complexes of gold(I) and gold(III). Crystal structures of [(dppf)AuPPh3]ClO4·CHCl3 and [(dppf)Au(μ-dppf)Au(dppf)](ClO4)2·2CH 2Cl2
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Displacement of tetrahydrothiophene in gold(I) complexes such as [AuX(tht)] or [Au(tht)L]ClO4 by the 1,1′-bis(diphenylphosphino)ferrocene ligand leads to the neutral [(dppf)(AuX)2] [X = C6F5 (1), Cl (2)] or cationic dinuclear complexes [(dppf)(AuL)2] (ClO4)2 [L = CH2PPh3 (3), CH2PPh2Me (4), CH2PPhMe2 (5)]. Other dinuclear complexes have been prepared by substitution reactions of compound 2, namely [(dppf)(AuL)2]n+ [L = SCN, n = 0 (6); L = tht, n = 2 (7)]. Three- and four-coordinated derivatives of the types [(dppf)AuCl] (8), [(dppf)(AuPR3)]ClO4[PR3 = PPh3 (9), PPh2Me (10)], [Au(dppf)2]ClO4 (11), and [(dppf)Au(μ-dppf)Au(dppf)](ClO4)2 (12) are obtained by reaction of the gold(I) precursor and the diphosphine. The reaction of equimolecular amounts of dppf and [Au(tht)2]ClO4 affords a mixture of the dinuclear linear complexes [Au(dppf)]2(ClO4)2 (13) and the mononuclear three-coordinated complex [(dppf)Autht]ClO4 (14). Similarly, by displacement of tht in [AuR3tht] or [AuR2(tht)2]ClO4 (R = C6F5) by the dppf ligand, the gold(III) derivatives [(dppf)AuR3] (15), [(dppf)(AuR3)2] (16), and [(dppf) AuR2]ClO4 (17) can be synthesized. Cyclic voltammetry of some of the compounds reveals one chemically reversible phosphinoferrocene-based oxidation. Single-crystal X-ray structure determinations were performed for complexes 9 and 12. [(dppf)(AuPPh3)]ClO4 (9) crystallizes in space group P21/c, monoclinic, with a = 14.239(6) A?, b = 16.889(4) A?, c = 20.866(8) A?, β = 95.81(3)°, and Z = 4. [(dppf)Au(μ-dppf)Au(dppf)](ClO4)2 (12) crystallizes in space group C2/c, monoclinic, with a = 32.858(6) A?, b = 14.821(3) A?, c = 26.399(5) A?, β = 128.48(2)°, and Z = 4. The cation of 12 is exactly centrosymmetric. Both complexes show trigonal planar coordination at gold. The ferrocene rings are staggered by 18-36°.
- Gimeno, M. Concepción,Laguna, Antonio,Sarroca, Cristina,Jones, Peter G.
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p. 5926 - 5932
(2008/10/08)
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