- G0ld-Boron Chemistry. Part 1. Synthetic, Structural, and Spectroscopic Studies on the Compounds (R=cyclo-C6H11 or C6H4Me-2)
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The new Class of 2 gold-boron compounds (1a; R=cyclo-C6H11; 1b, R=C6H4Me-2) have been prepared by the reaction between and B10H14 in CH2Cl2.Compound (1a) is also afforded by reaction between > and (1-).The exact mechanism of the first reaction is unclear, but probably proceeds via sequential oxidative addition and reductive elimination.Crystallographic analyses of compounds (1) show the expected decarborane-like geometry.There is some evidence of an intramolecular interaction between Au and the B(9)-H-B(10) bridge system.A thorough n.m.r. study of (1b) was undertaken, including an 11B(COSY) experiment which allowed almost complete assignment of the ten inequivalent B atoms in the molecule.
- Wynd, Adrew J.,McLennan, Alistar J.,Reed, David,Welch, Alan J.
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- Synthesis of L-Au(I)-CF2H Complexes and Their Application as Transmetalation Shuttles to the Difluoromethylation of Aryl Iodides
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We describe herein two alternative protocols to efficiently prepare difluoromethylgold(I) complexes bearing ancillary ligands with different electronic and steric properties. LAu-OX (X = H andt-Bu) species, formed in the presence of base, have been identified as intermediate complexes involved in these transformations. The application of these compounds as “CF2H transmetalation shuttles” from gold to palladium has been demonstrated in a Pd-catalyzed difluoromethylation reaction of aryl iodides, in which the Au-to-Pd transfer of “CF2H” is feasible under stoichiometric conditions. These findings will pave the way for catalytic manifolds in gold chemistry.
- García-Domínguez, Patricia
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p. 2923 - 2928
(2021/09/07)
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- Systematically Tuning the Electronic Structure of Gold Nanoclusters through Ligand Derivatization
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While the ability to crystallize metal nanoclusters has revealed their geometric structure, the lack of a similarly precise measure of their electronic structure has hampered the development of synthetic design rules to precisely engineer their electronic properties. We track the evolution of highly-resolved electronic absorption spectra of gold nanoclusters with precisely mass-selected chemical composition in a controlled environment. Simple derivatization of the ligands yields larger spectral changes than varying the overall atomic composition of the cluster for two clusters with similar symmetry and size. The nominally metal-localized HOMO–LUMO transition of these nanoclusters lowers in energy linearly with increasing electron donation from the exterior of the ligand shell for both cluster sizes. Very weak surface interactions, such as binding of He or N2, yield significant state-dependent shifts, identifying states with significant interfacial character. These observations demonstrate a pathway for deliberate tuning of interfacial chemistry for chemical and technological applications.
- Cirri, Anthony,Morales Hernández, Hanna,Kmiotek, Christina,Johnson, Christopher J.
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supporting information
p. 13818 - 13822
(2019/08/22)
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- Aurophilicity in action: Stepwise formation of dinuclear Au(i) macrocycles with rigid 1,8-dialkynylanthracenes
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Two phosphane-gold(i) functions (with tri(para-tolyl)- or tri-n-butylphosphane) were attached to a 1,8-diethynylanthracene backbone. The ligand size prevents direct interaction between the gold atoms, but the initial products rearrange to form macrocyclic
- Niermeier, Philipp,Wickemeyer, Lucas,Neumann, Beate,Stammler, Hans-Georg,Goett-Zink, Lukas,Kottke, Tilman,Mitzel, Norbert W.
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supporting information
p. 4109 - 4113
(2019/04/01)
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- Photosensitizer-Free, Gold-Catalyzed C–C Cross-Coupling of Boronic Acids and Diazonium Salts Enabled by Visible Light
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The first photosensitizer-free visible light-driven, gold-catalyzed C–C cross-couplings of arylboronic acids and aryldiazonium salts are reported. The reactions can be conducted under very mild conditions, using a catalytic amount of tris(4-trifluoromethyl)phosphinegold(I) chloride [(4-CF3-C6H4)3PAuCl] with methanol as the solvent allowing an alternative access to a variety of substituted biaryls in moderate to excellent yields with broad functional group tolerance. (Figure presented.).
- Witzel, Sina,Xie, Jin,Rudolph, Matthias,Hashmi, A. Stephen K.
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supporting information
p. 1522 - 1528
(2017/05/05)
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- Oxidative Addition to Gold(I) by Photoredox Catalysis: Straightforward Access to Diverse (C,N)-Cyclometalated Gold(III) Complexes
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Herein, we report the oxidative addition of aryldiazonium salts to ligand-supported gold(I) complexes under visible light photoredox conditions. This method provides experimental evidence for the involvement of such a process in dual gold/photoredox-catalyzed reactions and delivers well-defined (C,N)-cyclometalated gold(III) species. The remarkably mild reaction conditions and the ability to widely vary the ancillary ligand make this method a potentially powerful synthetic tool to access diverse gold(III) complexes for systematic studies into their properties and reactivity. Initial studies show that these species can undergo chloride abstraction to afford Lewis acidic dicationic gold(III) species.
- Tlahuext-Aca, Adrian,Hopkinson, Matthew N.,Daniliuc, Constantin G.,Glorius, Frank
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supporting information
p. 11587 - 11592
(2016/08/05)
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- Efficient general procedure to access a diversity of gold(0) particles and gold(I) phosphine complexes from a simple HAuCl4 source. Localization of homogeneous/heterogeneous system's interface and field-emission scanning electron microscopy study
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Soluble gold precatalysts, aimed for homogeneous catalysis, under certain conditions may form nanoparticles, which dramatically change the mechanism and initiate different chemistry. The present study addresses the question of designing gold catalysts, taking into account possible interconversions and contamination at the homogeneous/heterogeneous system's interface. It was revealed that accurate localization of boundary experimental conditions for formation of molecular gold complexes in solution versus nucleation and growth of gold particles opens new opportunities for well-known gold chemistry. Within the developed concept, a series of practical procedures was created for efficient synthesis of soluble gold complexes with various phosphine ligands (R3P)AuCl (90-99% yield) and for preparation of different types of gold materials. The effect of the ligand on the particles growth in solution has been observed and characterized with high-resolution field-emission scanning electron microscopy (FE-SEM) study. Two unique types of nanostructured gold materials were prepared: hierarchical agglomerates and gold mirror composed of ultrafine smoothly shaped particles.
- Zalesskiy, Sergey S.,Sedykh, Alexander E.,Kashin, Alexey S.,Ananikov, Valentine P.
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supporting information
p. 3550 - 3559
(2013/05/09)
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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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- The first metal complexes derived from 3,5-diethynylpyridine. X-ray crystal structure of [(AuPTo3)2{μ-(C=C)2Py}] (Py = pyridine-3,5-diyl; to = p-toly1)
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The reactions of 3,5-diethynylpyridine (Py(C=CH)2) with PPN[Au(acac) 2] (2.5:1; PPN = Ph3P=N=PPh3) or with [AuCl(SMe2)] and NEt3 (1:2:2) give respectively PPN[Au{C=C(Py)-C=CH}2] (1) and [Au2{μ-(C=C) 2Py}]n (2). Complex 2 reacts with monodentate ligands (1:2) or with 1,6-bis(diphenylphosphino)hexane (dpph, 1:1) to give neutral dinuclear complexes of the general formula [(AuL)2{μ-(C=C) 2Py}] (L = CN'Bu (3), PMe3 (4), PPh3 (5), PTo3 (To = CeH4Me-4) (6); Au2L 2 = Au2(μ-dpph) (7)). The reactions of 6 with the complexes [MCI] and TITfO (1:1:1) (TfO = CF3SO3) give the cationic trinuclear complexes [M{Py(C=CAuPTo3)2}]TfO (M = AuPTo3 (8), cis-PtCl(PPh3)2 (9)). The crystal structure of complex 6 has been determined.
- Vicente, Jose,Chicote, Maria-Teresa,Alvarez-Falcon, Miguel M.,Bautista, Delia
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p. 5707 - 5712
(2008/10/09)
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- Mixed ligand gold(I) complexes of phosphines and thiourea and X-ray structure of (thiourea-κS)(tricyclohexylphosphine)gold(I)chloride
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A series of mixed ligand gold(I) complexes with thiourea (Tu) and various phosphines, [R3PAuTu]Cl, have been prepared and characterized by elemental analysis, IR and NMR (13C, 15N and 31P) spectroscopies and X-ray crystallography. The spectral data of all complexes are consistent with the sulfur coordination of thiourea to gold(I). The single crystal X-ray structure of the complex [Cy3P-Au-Tu]Cl revealed that the geometry is not perfectly linear at the gold(I) with a P-Au-S bond angle of 168.54(9)°. The Au-P and Au-S distances are 2.274(2) and 2.295(2) A?, respectively.
- Isab, Anvarhusein A.,Fettouhi, Mohammed,Ahmad, Saeed,Ouahab, Lahcène
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p. 1349 - 1354
(2008/10/08)
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- Heterobimetallische 2-(Dimethylaminomethyl)ferrocenyl-Derivate des einwertigen Goldes
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[2-(dimethylaminomethyl)ferrocenyl]-lithium, FcNLi (I) reacts with gold (I) complexes ClAu·L to heterobimetallic organo gold(I) compounds (FcN)Au·L [L=P(C6H3F2-m,p)3 (1), P(C6H3F2/sub
- Jacob, Klaus,Voigt, Frank,Merzweiler, Kurt,Wagner, Christoph,Zanello, Piero,Fontani, Marco,Pietzsch, Claus
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p. 265 - 276
(2007/10/03)
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- Late transition metal oxo and imido complexes. II. Gold(I) oxo complexes
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The gold(I) oxo complexes [(LAu)3(μ3-O)] BF4 (1) have been prepared for L = PMePh2, PMe2Ph, PEtPh2, PPriPh2, P(p-ClPh)3, P(o-tol)3, P(OEt)Ph2, and P(OMe)3. Two of these new oxo complexes, as well as a new crystal form of [(PPh3Au)3(μ3-O)]BF4, were structurally characterized. Crystals of [(PMePh2Au)3(μ3-O)]BF 4·CH2Cl2 from CH2Cl2/ether are monoclinic (P21/c) with a= 11.395(2) A?, b = 25.901(2) A?, c = 16.024(3) A?, β = 110.615(8)°, and Z = 4. Crystals of [(PPh3Au)3(μ3-O)]BF 4·1.5CH2Cl2 from CH2Cl2/ether are monoclinic (P21/c) with a = 14.723(3) A?, b = 14.808(3) A?, c = 25.999(3) A?, β = 104.06(3)°, and Z = 4. Crystals of [(P(O-tol)3Au)3(μ3-O)]BF 4·xC6H14·0.5H2O from CH2Cl2/hexane are monoclinic (P21/a) with a = 14.2611(45) A?, b = 27.4668(71) A?, c = 23.0907(81) A?, β = 91.37(2)°, and Z = 4. The PPh3 and the PMePh2 structures consist of inversion-related edge-bridged [(LAu)3O]+ dimers held together by Au-Au interactions. The P(o-tol)3 structure consists of isolated [(LAu)3O]+ units. New oxo complexes are also formed in equilibrium mixtures of [((PPh3)Au)3(μ3-O)]BF4 and LAuCl. Oxygen-17 NMR data for 1 show chemical shifts of +19.7 to -36.0 ppm (H2O reference) with upfield shifts corresponding to increasing basicity of the phosphine, L.
- Yang, Yi,Ramamoorthy, Visalakshi,Sharp, Paul R.
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p. 1946 - 1950
(2008/10/08)
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- To fuse or not to fuse? Reactions of [HM4(CO)12BH]- (M = Fe, Ru) with (phosphine)gold(I) chlorides. Molecular structures of HFe4(CO)12BHAuP(2-Me-C6H4) 3, [Au(PMePh2)2][{HFe4(CO)12BH} 2Au], and [PPN][{HRu4(CO)12BH}2Au]
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The reaction of [HFe4(CO)12BH][PPN] (PPN = bis(triphenylphosphine)nitrogen(1+)) with 1 equiv of LAuCl (L = P(2-Me-C6H4)3, P(c-C6H11)3) yields HFe4(CO)12BHAuL, but of these two products only HFe4(CO)12BHAuP(2-Me-C6H4) 3 (1) is stable in solution. Attempts to prepare other monogold derivatives with L = PMe3, PEt3, PMe2Ph, PMePh2 led instead to the ionic product [AuL2][{HFe4(CO)12BH}2Au] ([AuL2][4]), which possesses the same stoichiometry as the target molecule HFe4(CO)12BHAuL but is produced as a result of Au-P bond cleavage and a ligand redistribution reaction. The ruthenium cluster HRu4(CO)12BHAuP(2-Me-C6H4) 3 (2) may be prepared by a corresponding route to that used for 1, but unlike 1, formation of 2 competes not only with formation of [AuL2][{HRu4(CO)12BH}2Au] ([AuL2][5]) but also with that of the digold derivative Ru4(CO)12BHAu2{P(2-Me-C6H 4)3}2 (3). Both 1 and 2 are readily deprotonated by NEt3 with loss of Fe-H-Fe or Ru-H-B protons, respectively. Treatment of [HFe4(C-O)12BH][PPN] with ClAu(dppm)AuCl (dppm = bis(diphenylphosphino)methane) leads to a mixture of the borido cluster HFe4(CO)12Au2(dppm)B (6; 40%) and the salt [PPN][{HFe4(CO)12BH}2Au] ([PPN][4]; 30%), while in the analogous reaction of [HRu4(CO)12BH][PPN] with ClAu(dppm)AuCl, the predominant cluster product is [PPN][5]. The observed results are discussed in terms of (i) the differing sizes of the Fe4 and Ru4 butterfly frameworks and (ii) the steric constraints of the phosphine ligands. The molecular structures of 1, [Au(PMePh2)2][4], and [PPN][5] are presented. 1: triclinic, P1; a = 10.023 (2) ?, b = 12.814 (3) ?, c = 15.231 (4) ?; α = 104.02 (2),° β = 90.47 (2)°, γ = 90.13 (2)°; V = 1897.8 (9) ?3; Z = 2; R(F) = 4.41%. [Au(PMePh2)2][4]: monoclinic, C2/c; a = 21.704 (3) ?, b = 9.542 (2) ?, c = 29.717 (6) ?; β = 97.50 (1)°; V = 6102.0 (19) ?3; Z = 4; R(F) = 4.59%. [PPN][5]: triclinic, P1; a = 9.759 (4) ?, b = 13.898 (5) ?, c = 26.964 (17) ?; α = 96.68 (4)°, β = 97.31 (4)°, γ = 91.78 (4)°; V = 3599 (3) ?3; Z = 2; R(F) = 7.65%. The structure of each of the anions [4]- and [5]- exhibits two cluster subunits fused together in a face-to-face orientation via a single gold atom. In [4]- the subunits are mutually cis and there is a spiro twist of 30.9 (5)° at the gold atom. However, in [5]-, the cluster subunits are arranged in a trans configuration, as would be expected on the basis of steric arguments.
- Draper, Sylvia M.,Housecroft, Catherine E.,Rees, Jacqueline E.,Shongwe, Musa S.,Haggerty, Brian S.,Rheingold, Arnold L.
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p. 2356 - 2367
(2008/10/08)
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