- Electrophilic additions of mono-, di- and tri-gold units to the isoelectronic 2- and 2- anions
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The reaction of 2 with or in tetrahydrofuran gives the mixed manganese-gold clusters 3-H)(μ-AuPR3)> (R = Ph (1) or Me (2)) and 23-H)Au>2(μ-diphos)> (diphos = dppe (3) or dppm (4)).The reaction between the same manganese anion and produces 3-H)Au>3(triphos)>3- (5), 3-H)Au>2(triphos)(AuCl)>2- (6) or 3-H)Au>(triphos)(AuCl)2>- (7), depending on the molar ratio of the reagents.Isoelectronic iron-goldcomplexes (3-x)(triphos)(AuCl)x>(3-x)- (x = 0 (8), 1 (9) or 2 (10) were obtained by the reaction of the trinuclear 2- anion with in the appropriate molar ratio.Attempts to obtain mixed manganese-iron-gold clusters resulted in a mixture of compounds, the nature of which has been explained in terms of metal-ligand redistribution processes.Keywords: Gold; Manganese; Iron; Metal-metal bonds; Clusters; Electrophilic addition
- Rossell, Oriol,Seco, Miquel,Segales, Gloria
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- Luminescent gold(i) macrocycles with diphosphine and 4,4'-bipyridyl ligands
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The complexes [{-Ph2P(CH2)aPPh2AuNC5H4C5H4NAu-y2l:+ [CF3CVL (/; = 1-6) were prepared as colourless, air-stable solids by reaction of silver trifluoroacetate with the corresponding precursor complex [(CH2)(Ph2PAuCl)2], and
- Brandys, Marie-Claude,Jennings, Michael C.,Puddephatt, Richard J.
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Read Online
- 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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supporting information
p. 634 - 637
(2017/08/15)
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- Method for preparing organic phosphonic gold chloride (I) compound
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The invention discloses a method for preparing an organic phosphonic gold chloride (I) compound. The method comprises the following steps: (1) adding chloroauric acid hydrated salt into a reaction container, dissolving with water, and uniformly stirring in an ice-water bath; (2) keeping the temperature of the ice water in the reaction container, dripping a glucosinolates diaryl compound or a derivative of the glucosinolates diaryl compound, and stirring uniformly; (3) dripping a mixed liquid of phosphine-containing ligand and ethanol into the reaction container one droplet by one droplet, removing the ice-water bath, recovering the room temperature naturally, and stirring for 2-5 hours; (4) stopping stirring, performing suction filtration, washing with cold methanol, dissolving the collected solid with an organic solvent, and performing suction filtration again so as to remove insoluble matters; (5) performing concentration spinning drying on the solution, recrystallizing with a solvent, and performing suction filtration again, thereby obtaining the organic phosphonic gold chloride (I) compound. As the glucosinolates diaryl compound or the derivative of the glucosinolates diaryl compound is taken as a reduction reagent, and due to reaction between the chloroauric acid hydrated salt and the phosphine-containing ligand in an ethanol-water system, environment-friendly, safe and efficient production of the organic phosphonic gold chloride (I) compound can be achieved, and moreover, industrial application of the organic phosphonic gold chloride (I) compound is facilitated.
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Paragraph 0055; 0056; 0057; 0058; 0059; 0060
(2016/12/16)
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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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- 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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p. 9810 - 9820
(2011/12/03)
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- Polymeric and macrocyclic gold(I) complexes with bridging dithiolate and diphosphine ligands
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The reaction of digold(I) diphosphine complexes [Au2(O2CCF3)2(μ-Ph2P-X -PPh2)] with dithiols HS-Y-SH can give either macrocyclic complexes [Au2(μ-S-Y-S)(μ-Ph2P-X-PPh2)] or polymeric complexes [Au2(μ-S-Y-S)(μ-Ph2P-X-PPh2)] n. The structures of the macrocyclic complex [Au2{μ-(S-4-C6H4)2S}{μ -Ph2P(CH2)4PPh2}], and the polymeric complexes [Aun{μ-(S-CH2CO2CH2CH 2O)2-1,4-C6H4}n(μ- trans-Ph2PCH{double bond, long}CHPPh2)n] and [Aun{μ-(S-CH2CO2CH2CH 2O)2-1,5-C10H6}n(μ -trans-Ph2PCH{double bond, long}CHPPh2)n] have been determined. Evidence is presented that the complexes exist primarily as macrocycles in solution and that, in favorable cases, ring-opening polymerization occurs during crystallization.
- Hunks, William J.,Jennings, Michael C.,Puddephatt, Richard J.
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p. 3605 - 3616
(2008/10/09)
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- Binary and ternary cluster complexes containing gold-selenium, gold-indium-selenium and gold-gallium-tellurium
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Reactions of gold phosphane complexes [(AuX)(PR3)] (X = Cl, Br, I; R = organic moiety) with Se(SiMe3)2 lead to the formation of gold complexes with chalcogenide bridges. The reaction of the complex [Ph3PAuCl] and tBuSe(SiMe3) gives the cluster [Au5Se2(PPh3)4]Cl (1). The in situ preparation of the complex [(AuCl)2dpph] [dpph = Ph 2P(CH2)6PPh2] by reaction of dpph with [Me2SAuCl], and subsequent reaction with Se(SiMe 3)2, leads to the formation of [(Au3Se) 2(dpph)3]Cl2 (2). Reactions of the gold(I) complex [(AuCl)2dpppe] [dpppe = Ph2P(CH2) 5PPh2] with Se(SiMe3)2 and InCl 3 in different molar ratios lead to the formation of [Au 10Se4(dpppe)4]InCl5 (3) and [Au 4(SeInCl3)2(dpppe)2] (4). The reaction of [(AuCl)2dpph] with Te(SiMe3)2 and GaCl3 produces the isostructural cluster compound [Au 4(TeGaCl3)2(dpph)2] (5). From the reaction of Se(SiMe3)2 with [(AuCl)2dppe] [dppe = Ph2P(CH2)2PPh2] and InCl 3 [Au8Se4In(dppe)4](InCl 4)3 6 can be isolated. The structures of 1-6 were determined by X-ray diffraction. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
- Olkowska-Oetzel, Jolanta,Sevillano, Paloma,Eichhoefer, Andreas,Fenske, Dieter
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p. 1100 - 1106
(2007/10/03)
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- N-Metallation of MS2N2 rings. X-ray crystal structures of [(η5-C5Me5)Ir(S 2N2)Au(PPh3)][ClO4], [{η 5-C5Me5Ir(S2N2)Au} 2 (μ2-dppm)][ClO4]2 and [Au(dppeS-P)Cl]2
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Bimetallic complexes [(η5-C5R5) M(S2N2)Au(PPh3)][ClO4] and tetrametallic species [{(η5-C5R5) M(S 2N2)Au}2(μ2-P^P)][ClO 4]2 (R = H, M = Co; R = Me, M = Ir; P^P = dppm or dppe) can be prepared by treatment of [(η5-C5R 5)M(S2N2)] with gold(I) electrophiles generated by chloride abstraction from [AuCl(PPh3)] or [(AuCl) 2(μ2-P^P)]. X-Ray crystallography of [(η5-C 5Me5) Ir(S2N2)Au(PPh 3)][ClO4] and [{(η5-C5Me 5)Ir(S2N2)Au}2(η 2-dppm)][ClO4]2 confirms auration of the metal-bound nitrogen atom of the MS2N2 ring. π-Stacking of theMS2N2 rings occurs within both structures.
- Aucott, Stephen M.,Bhattacharyya, Pravat,Milton, Heather L.,Slawin, Alexandra M. Z.,Woollins, J. Derek
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p. 1466 - 1469
(2007/10/03)
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- Synthesis, characterization and electrochemical studies of the heterometallic diclusters [{Fe2(μ-CO)(CO)6(μ-PPh2)Au}2(d iphosphine)] (diphosphine=dppm, dppip, dppe, dppp)
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Treatment of [(ClAu)2(diphosphine)] {diphosphine=bis(diphenylphosphino)methane (dppm), bis(diphenylphosphino)isopropane (dppip), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp)} with two equivalents of the anion [Fe2(μ-CO)(CO)6(μ-PPh2)]- in the presence of TlBF4 gives the new heterometallic diclusters [{Fe2(μ-CO)(CO)6(μ-PPh2)Au}2(d iphosphine)] that have been isolated and characterized. Their 31P-NMR spectra show different patterns as a function of the diphosphine ligand. The electrochemical behavior of these compounds has been investigated and compared with that of the mono- [Fe2(μ-CO)(CO)6(μ-PPh2)(μ-AuPPh3)] and tricluster [{Fe2(μ-CO)(CO)6(μ-PPh2)Au}3(t riphos)] derivatives.
- Ferrer, Montserrat,Julia, Anna,Reina, Roser,Rossell, Oriol,Seco, Miquel,De Montauzon, Dominique
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p. 147 - 153
(2007/10/03)
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- Ionic complexes [Au2(P-P)2][Co(CO)4]2 as intermediates in the synthesis of compounds containing a Co2 Au2 core
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The pathway for the formation of [Co2 Au2(CO)6( μ-dppm)2] (3) from dppm and [{(CO)4CoAu}2( μ-dppm)] (2a) seems to involve the intermediate complex [Au2( μ-dppm)2][Co(C
- Pons, Angels,Rossell, Oriol,Seco, Miquel,Solans, Xavier,Font-Bardia, Merce
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p. 177 - 182
(2007/10/03)
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- Chemistry of Polynuclear Metal Complexes with Bridging Carbene or Carbyne Ligands. Part 114. Ditungsten-Digold Compounds having two W(CC6H4Me-4)(CO)2(η5-C2B9H9Me2) Fragments linked by AuP(Ph)2(CH2)n(Ph)2PAu (n = 2-6) Groups
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Treatment of 1 equivalent of the reagent CR)(CO)2(η5-C2B9H9Me2)> (R = C6H4Me-4), in the presence of TlBF4, with 0.5 equivalent of the compounds > (n = 2-6) in CH2Cl2 affords the complexes (CO)4(η5C2B9H9Me2)2>.The crystal structure of the species with n = 4 has been determined by X-ray crystallography, confirming that the molecule has two RCW(CO)2(η5-C2B9H9Me2) fragments bridged by an AuP(Ph)2CH2CH2CH2CH2(Ph)2PAu unit, with a centre of inversion at the midpoint of the chain of methylene groups.The W-Au bonds are asymmetrically bridged by the p-tolylmethylidyne ligands .In a similar manner, the compounds 5-C2B9H9Me2)2> have been prepared from reactions between the gold compounds and the salt CR)(CO)2(η5-C2B9H9Me2)>.Addition of (cod = cycloocta-1,5-diene) to the complexes (CO)4(η5C2B9H9Me2)2> affords the chain cluster compounds 3-CR)2(μ-Ph2P(CH2)nPPh2>(CO)4(cod)2(η5-C2B9H9Me2)2>.The NMR data (1H, 13C-, 31P- and 11B- for the new complexes are reported and discussed.
- Goldberg, Justin E.,Mullica, Donald F.,Sappenfield, Eric L.,Stone, F. Gordon A.
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p. 2495 - 2502
(2007/10/02)
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- Gold(I) complexes with bidentate tertiary phosphine ligands: Formation of annular vs. tetrahedral chelated complexes
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Titrations of gold(I) complexes [(AuCl)2(P-P)] with ligand (P-P) were studied by 31P NMR for the bidentate tertiary phosphine ligands Ph2P(CH2)nPPh2, where n = 1 (dppm), 2 (dppe), 3 (dppp), and 4 (dppb), cis-Ph2PCH=CHPPh2 (dppey), Ph2P(CH2)2PEt2 (eppe), and Et2P(CH2)2PEt2 (depe). Bis-chelated four-coordinate gold(I) phosphine complexes [Au(P-P)2]+ containing either five- or six-membered chelate rings (n = 2 or 3) all exhibited exceptionally high thermodynamic and kinetic stabilities in solution. The species containing phenyl-substituted phosphines existed in CDCl3 solutions at Au:P-P ratios of less than 1:1. They were isolated and characterized with Cl- as the counteranion. [Au(depe)2]+ existed in solution at Au:depe ratios >1:1 and was isolable as a PF6- or SbF6- salt. Four-coordinate complexes containing either four- (n = 1) or seven-membered (n = 4) chelate rings were not observed as stable species in CDCl3 solutions. The solution behavior of species with a 1:1 Au:P-P ratio was also investigated by 31P NMR. In D2O the 31P NMR spectrum of the 1:1 Au:eppe species consisted of two overlapping AA′BB′ multiplets corresponding to the two isomers of the annular complex [Au2(eppe)2]2+. The isomer containing two Et2P-Au-PPh2 linkages (X) predominated by 2:1 over the other isomer (Y). For the ligands dppe and eppe, the 1:1 Au:P-P complexes were stable in aqueous solution but were involved in dissociative equilibria in CDCl3 with ring-closed species. The analogous complexes of depe, dppm, and dppb appeared to be stable in chloroform. These observations are discussed in terms of a destabilization of the annular [Au2(P-P)2]2+ complexes by steric effects.
- Berners-Price, Susan J.,Sadler, Peter J.
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p. 3822 - 3827
(2008/10/08)
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- Stable Gold(I) Complexes with Chelate Rings: Solution Studies of Bis(phosphino)ethane Complexes and X-Ray Crystal Structure of Bisgold(I) Hexafluoroantimonate-Acetone (1/1)
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Bis-chelated four-co-ordinate gold(I)-phosphine complexes of 1,2-bis(diphenylphosphino)ethane (dppe) and 1,2-bis(diethylphosphino)ethane (depe) exhibit exceptionally high thermodynamic and kinetic stability both in the solid state and in solution at ambient temperatures.Their formation in solution has been studied by conductivity and 31P n.m.r. titrations.Complexes of (1+) and (1+) have been prepared and characterized.These species exist in solution even at Au:bis(phosphine) ligand ratios of 1:0.75.The mixed species (1+) exhibited a trans-gold 31P-31P n.m.r. coupling of 52 Hz.The title complex was crystallized and shown by X-ray crystallography to contain gold (I) with a flattened tetrahedral (closely D2d) co-ordination geometry (P-Au-P, 85-130) chelated by two dppe ligands with Au-P bond lengths of 2.39-2.42 A.Crystals are monoclinic, space group P21/n, with a=18.685(2), b=19.414(2), c=15.096(1) A, β=91.69(1), and Z=4; 4 811 reflections refined to R 0.062.
- Berners-Price, Susan J.,Mazid, Muhammed A.,Sadler, Peter J.
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p. 969 - 974
(2007/10/02)
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- Cyclic μ-(4-Methylcyclohexadien-1-ylidenio)-bis Cations
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Arylation of α,ω-bisalkanes 1b - d using p-tolyllithium yields the binuclear tolylgold compounds 2n with n = 2, 3, and 4 (2b - d). p-CH3C6H4AuP(CH3)3 was obtained similarly as an NMR reference compound. 2d is converted into the cation p-CH3C6H42+ BF4- on treatment with HBF4 in diethyl ether, with elimination of toluene.The product is ascribed the cyclic structure 3d, based on NMR and 197Au Moessbauer data.
- Schmidbaur, Hubert,Inoguchi, Yoshio
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p. 1646 - 1653
(2007/10/02)
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