21209-78-9Relevant academic research and scientific papers
Comparing Protonolysis and Transmetalation Reactions: Microcalorimetric Studies of C-AuI Bonds in [AuRL] Complexes
Pérez-Iglesias, María,Espinet, Pablo,Casares, Juan A.
, p. 11193 - 11200 (2018)
The protonolysis of C-Au bonds in [AuRL] organometallic complexes has been studied by calorimetry for 12 R groups. The experimental data have been combined with density functional theory calculations to obtain bond dissociation energy (BDE) values. The C-Au BDE values show a good correlation with the corresponding isolobal C-H BDE values. The heat released in the protonolysis of [AuRL] has also been measured for R = Ph and L = P(OPh)3, PPh3, PMe3, PCy3, and IPr, and these values strongly depend on the trans influence of L because of the mutual destabilization of the L-Au and Au-C bonds. The enthalpies of the transmetalation reaction [AuR(PPh3)] + SnIBu3 → [AuI(PPh3)] + SnRBu3 for seven R groups have been measured and compared with those of the corresponding [AuR(PPh3)] protonolysis.
Bridging phenyl ligands. Unsaturated mercury-triosmium carbonyl cluster complexes containing bridging phenyl ligands
Adams, Richard D.,Luo, Zhongwen,Wong, Yuen Onn
, p. 46 - 51 (2015)
Abstract The gold phosphine group in the complex Os3(CO)10(μ-η1-Ph)(μ-AuPPh3), 1 can be replaced by mercury halide groups by reactions with mercury halides. The reaction of 1 with HgI2 yielded the new
Facile method of halogen exchange between Au(Cl)(L) and MeC(O)X (L = PPh3 and IPr; X = Br and I) via ?-bond metathesis supported by DFT calculation
Sanagawa, Atsushi,Kuniyasu, Hitoshi,Iwasaki, Takanori,Kambe, Nobuaki,Bobuatong, Karan,Ehara, Masahiro
supporting information, p. 831 - 832 (2013/09/02)
Complexes with the formula Au(X)(L) (X = Br and I; L = PPh3 and IPr) were conveniently prepared by a quite simple procedure using the treatment of Au(Cl)(L) with MeC(O)X and the subsequent evaporation under reduced pressure. The mechanistic study by DFT calculation with M06 functional supported that the reaction proceeded through σ-bond metathesis where Cl atom underwent a more roundabout course than Br atom did.
Studies of the structures and bonding of gold-bridged dirhenium carbonyl cluster complexes
Adams, Richard D.,Wong, Yuen Onn,Zhang, Qiang
, p. 7540 - 7546 (2014/04/03)
The compounds Re2(CO)8(μ-AuPPh3) 2, 1, a dimer of Re(CO)4(μ-AuPPh3), and ax,ax-Re2(CO)8(PPh3)2 were obtained from UV-vis radiation-induced decarbonylation of the compound Re(CO) 5[Au(PPh3)]. Compound 1 contains two rhenium atoms bridged by two AuPPh3 groups. The complex has 32 valence electrons and is formally unsaturated by the amount of two electrons. The Re-Re bond distance in 1 is unusually short (Re-Re = 2.9070(3) A), as found by a single-crystal structural analysis. The nature of the metal-metal bonding in 1 was investigated by DFT computational analyses, which have provided evidence not only for σ-bonding but also significant complementary π-bonding directly between the two rhenium atoms. The electronic structure of Re2(CO) 8(μ-H)2, 2, was similarly analyzed and is compared with that of 1. Compound 1 is intensely colored due to low-energy, metal-based electronic transitions between the HOMO and HOMO-2 and the LUMO. Compound 1 reacts with I2 to yield Re2(CO)8(μ- AuPPh3)(μ-I), 3, and the known compound Re2(CO) 8(μ-I)2, 4, by substitution of the bridging AuPPh 3 groups with bridging iodide ligands. Compound 3 is electronically saturated, 34 valence electrons, and contains a formal Re-Re single bond: Re-Re = 3.2067(5) A. Compound 3 was also in a high yield (83%) from the reaction of Re2(CO)8(μ-H)(μ-CH=CHC4H9) with Au(PPh3)I. The Re-Re bonding in compounds 3, 4, and Re 2(CO)10 was also analyzed computationally, and this bonding was compared with their bonding in 1 and 2.
Tuneable reactivity with PPh3 and SnX2 of four- and five-coordinate Pd(ii) and Pt(ii) complexes containing polyphosphines
Fernandez-Anca, Damian,Garcia-Seijo, M. Ines,Garcia-Fernandez, M. Esther
, p. 10221 - 10232 (2013/07/26)
The reactivity of the unusual d8 trigonal-bipyramidal systems [MX(PP3)]X (X = Cl: M = Pd(1a), Pt(2a); X = Br: M = Pd(3a), Pt(4a); X = I: M = Pd(5a), Pt(6a); PP3 = tris[2-(diphenylphosphino)ethyl] phosphine) in CHCl3-CH3OH, the square-pyramidal compounds [MCl(NP3)]Cl (M = Pd(7a); Pt(8a); NP3 = tris[2-(diphenylphosphino)ethyl]amine) in CD3OD-DMF and the distorted square-planar mononuclear [MX(PNP)]X (M = Pd: X = Cl(10a); M = Pt: X = I(10b); PNP = bis[2-(diphenylphosphino)ethyl]amine) and the heteronuclear [PdAu 2X4(PP3)] [X = I(9a), Cl(14a), Br(15a)] and [MAuX2(PP3)]X [M = Pd: X = Cl(16a); M = Pt: X = Cl(17a), Br(18a)] species in CDCl3 with PPh3 + SnX2 has been explored to establish the factors that influence the nature of the products. With the mononuclear precursors the course of the reaction is strongly dependent on the tripodal or linear arrangement of the polydentate ligand and in the former case on the halogen. Thus, while for chlorides (1a-2a, 7a-8a) and bromides (3a-4a) the reaction led to the trigonal-bipyramidal compounds [M(SnCl3)(AP3)][SnCl3] [A = P: M = Pd(1), Pt(2); A = N: M = Pd(7), Pt(8)], [MBr(PP3)][SnBr3] [M = Pd(4), Pt(6)] containing M-Sn and M-Br bonds, respectively, for iodides (5a-6a) resulted in the unknown neutral square-planar compounds [MI2(PP(PO) 2)(SnI2)2] [M = Pd(9) and Pt(10)] bearing two dangling PO-SnI2 units and P2MI2 environments. However, complexes of the type [PtCl(PP2PO)X]X′ [X = SnCl 2, X′ = [SnCl3]-(11)] and [M(PP(PO) 2)2X4]X′2 [X = SnCl 2, X′ = [SnCl3]-: M = Pd(12), Pt(13)] showing PO-SnCl2 arms were obtained by direct reaction of [PtCl(PP2PO)]Cl (11a) and [M(PP(PO)2)2]Cl 2 [M = Pd(12a), Pt(13a)] with SnCl2 in CH3OH. Although complex 9 was also prepared by interaction of the heteronuclear iodide 9a with PPh3 + SnI2 in CDCl3, the use of the neutral and ionic heteronuclear chlorides and bromides (14a-18a) as starting materials afforded the distorted square-planar ionic systems [MAuX′(PP3)(PPh3)][SnX3]2 [M = Pd: X = Cl, X′ = SnCl3-(14); X = Br, X′ = SnBr3-(15); M = Pt: X = Cl, X′ = SnCl 3-(17); X = Br, X′ = SnBr3 -(18)] containing M-SnX3 and P-Au-PPh3 functionalities. It was found that these reactions where the heteronuclear species are the precursors proceed via the trigonal-bipyramidal halides not only with X = Cl and Br(1a-4a) but also I(5a). When the precursors were 10a and 10b the reaction occurred with formation of [Pd(PNP)(PPh3)][SnCl 3]2 (23) and [Pt(PNP)(PPh3)][SnCl 2I]2 (24) showing M-PPh3 units and trihalostannato counter anions.
Effective transmetalation from gold to iron or ruthenium
Hashmi, A. Stephen K.,Molinari, Lise
, p. 3457 - 3460 (2011/09/12)
The transmetalation of aryl, alkynyl, and alkyl groups from organogold compounds to iron complexes offers an efficient synthesis of organoiron complexes under very mild conditions. This method could be extended to ruthenium complexes.
Gold and palladium combined for cross-coupling
Hashmi, A. Stephen K.,Lothschuetz, Christian,Doepp, Rene,Rudolph, Matthias,Ramamurthi, Tanuja D.,Rominger, Frank
, p. 8243 - 8246 (2010/02/27)
Gold and palladium-a unique liason: A study of the transmetalation abilities of organogold compounds builds the basis for a new class of cross-coupling reactions. Stable intermediates of gold catalysis deliver new complex products by a palladium-catalyzed coupling reaction, (see Scheme)
Synthesis and structures of 3-sila-β-diketiminato complexes of the coinage metals
Farwell, James D.,Hitchcock, Peter B.,Lappert, Michael F.,Protchenko, Andrey V.
, p. 4953 - 4961 (2008/03/13)
The dimeric copper(I) 3-sila-β-diketiminate [Cu{(N(R)C(Ar))2SiR}]2 · (thf) (1) was obtained from CuI and [Li{(N(R)C(Ar))2SiR}(thf)2] (B) in toluene (R = SiMe3, Ar = C6H3Me2-2,6). When [CuI(PPh3)3] was used as a starting material, the LiI-containing compound [Cu{Si(R)(C(Ar)N(R))2Li(μ-I)}(PPh3)] (2) was isolated. The reaction of [MI(PPh3)n] (M = Ag, n = 3; M = Au, n = 2) with two equivalents of B in toluene gave the isomorphous silver and gold 3-sila-β-diketiminates [M{Si(R)(C(Ar)N(R))2Li}2(μ-I)] [M = Ag (3), Au (4)]. Each of 1-4 was characterised by the multinuclear NMR spectroscopy and single-crystal X-ray diffraction crystallography.
The course of oxidative addition reactions of haloalkynes and haloalkenes to dimethyl- and dialkynylaurate(I) anions [RAuR]-
Schuster, Oliver,Schmidbaur, Hubert
, p. 3769 - 3775 (2008/10/09)
The reactions of halo-alkynes Cl-C{triple bond, long}CH, C-lC{triple bond, long}C-Cl or PhC{triple bond, long}C-I with solutions of Li+[MeAuMe]- in diethylether containing Ph3P do not give the expected oxidative addition products Me2(RC{triple bond, long}C)Au(PPh3) with R = H, Cl, Ph. A mixture of other complexes is obtained instead which are generated in secondary reactions involving reductive elimination of ethane and/or dialkyne. However, addition of the halo-alkene H(Cl)C{double bond, long}CCl2 to the same substrate solution affords trans-Me2[trans-H(Cl)C{double bond, long}C(Cl)]Au(PPh3) in good yield. Its molecular structure with pseudo-Cs symmetry has been determined by the solution NMR spectra and a single-crystal X-ray diffraction study. The reaction of methyl iodide with solutions of Li+[RC{triple bond, long}CAuC{triple bond, long}CR]- in diethylether containing PPh3 give the quaternary salts Ph3PMe+ [RC{triple bond, long}CAuC{triple bond, long}CR]- as the main products and only small amounts of cis-Me2(RC{triple bond, long}C)Au(PPh3) complexes probably formed in a series of oxidative addition, reductive elimination, and substitution reactions. The structure of Ph3PMe+ [PhC{triple bond, long}CAuC{triple bond, long}CPh]- has been determined.
Heteroatom-functionalized methylgold complexes: Synthesis and structure of chloromethyl(triphenylphosphine)- and phenylthiomethyl(trimethylphosphine)gold
Steinborn, Dirk,Becke, Steffi,Herzog, Renate,Guenther, Mike,Kircheisen, Robert,Stoeckli-Evans, Helen,Bruhn, Clemens
, p. 1303 - 1307 (2008/10/09)
[AuCl(PPh3)] reacts with Mg(CH2Cl)Cl, prepared in situ from CH2ClI and iPrMgCl, in ether at -65°C to give [Au(CH2Cl)(PPh3)] (1a), la reacts with LiI, NaOMe and PPh3 to give [Au(CH2I)(PPh3)] (2), [Au(CH2OMe)(PPh3)] (3) and [Au(CH2PPh3)(PPh3)]Cl (4), respectively. 2 decomposes rapidly at room temperature, yielding ethylene and [AuI(PPh3)]. The reaction of [AuCl(PMe3)] with LiCH2SPh in THF affords [Au(CH2SPh)(PMe3)] (5). The chloromethyl and the phenylthiomethyl complex 1a and 5 were isolated and characterized by NMR (1H, 13C, 31P) spectroscopy as well as by single-crystal X-ray structure analysis. In the solid state discrete molecules of 1a and 5 are found with linear C-Au-P units [C-Au-P 179,8(4)° (1a), 179,1(1)° (5)]. The angle Au-C-Cl (115,4(6)°) in 1a is slightly greater than the tetrahedral angle.
