- Crystal and Molecular Structures Of Two Complexes of Diphenyl(2-pyridyl)phosphine (L): and
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The reaction of the ligand diphenyl(2-pyridyl)phosphine (L) with HAuCl4 and AgCl affords the complexes and respectively.The crystal structures of these two complexes have been determined from fourcircle diffractometer data; is orthorombic, space group Pnma, with a=11.774(3), b=12.617(3), and 11.114(6) Angstroem, Z=4, and R=0.052 for 1358 observed reflections; is monoclinic, space group P21/c with a=14.599(3), b=18.388(5), and c=21.134(4) Angstroem, β=125.12(1) deg, Z=4, and R=0.060 for 5180 observed reflections.In the gold complex the phosphorus of L alone is bonded to the gold atom which assumes a linear geometry with Au-Cl 2.286(4) Angstroem and Au-P 2.234(4) Angstroem.The silver complex contains molecules in which two silver atoms are held together by two chloride bridges.One of the silver atoms is bonded to two L molecules through the phosphorus atom, while the other silver atom is bonded to a L molecule as well as loosely bonded to the nitrogen atom of one of the ligands co-ordinated to the first silver atom.The silver atoms assume a tetrahedral co-ordination with Ag-Cl 2.701(4), 2.618(8), 2.638(4), and 2.601(9) Angstroem; Ag-P 2.432(3), 2.436(4), and 2.452(3) Angstroem; and Ag-N 2.451(9) Angstroem.
- Alcock, Nathaniel W.,Moore, Peter,Lampe, Paul A.,Mok, K. F.
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- Impedance technology reveals correlations between cytotoxicity and lipophilicity of mono and bimetallic phosphine complexes
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Label free impedance technology enables the monitoring of cell response patterns post treatment with drugs or other chemicals. Using this technology, a correlation between the lipophilicity of metal complexes and the degree of cytotoxicity was observed. A
- Fonteh,Elkhadir,Omondi,Guzei,Darkwa,Meyer
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p. 653 - 667
(2015/07/08)
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- Structural evolution of atomically precise thiolated bimetallic [Au 12+ nCu32(SR)30+ n]4- (n = 0, 2, 4, 6) Nanoclusters
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A series of all-thiol stabilized bimetallic Au-Cu nanoclusters, [Au 12+nCu32(SR)30+n]4- (n = 0, 2, 4, 6 and SR = SPhCF3), are successfully synthesized and characterized by X-ray single-crystal analysis and density functional theory (DFT) calculations. Each cluster consists of a Keplerate two-shell Au12@Cu20 core protected by (6 - n) units of Cu2(SR)5 and n units of Cu2Au(SR)6 (n = 0, 2, 4, 6) motifs on its surface. The size and structural evolution of the clusters is atomically controlled by the Au precursors and countercations used in the syntheses. The clusters exhibit similar optical absorption properties that are not dependent on the number of surface Cu2Au(SR)6 units. Although DFT suggests an electronic structure with an 18-electron superatom shell closure, the clusters display different thermal stabilities. [Au12+nCu32(SR) 30+n]4- clusters with n = 0 and 2 are more stable than those with n = 4 and 6. Moreover, an oxidation product of the clusters, [Au 13Cu12(SR)20]4-, is structurally identified to gain insight into how the clusters are oxidized.
- Yang, Huayan,Wang, Yu,Yan, Juanzhu,Chen, Xi,Zhang, Xin,H?kkinen, Hannu,Zheng, Nanfeng
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supporting information
p. 7197 - 7200
(2014/06/09)
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- Heteropolynuclear gold complexes with metallophilic interactions: Modulation of the luminescent properties
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Metalloligands of stoichiometry [AuCl(P-N)] have been obtained by the reaction of the heterofunctional phosphines P-N = PPh2py, PPh 2CH2CH2py, or PPhpy2 with [AuCl(tht)] (tht = tetrahydrothiophene). Reactions of these metalloligands with several metal compounds have afforded heteropolynuclear species which exhibit luminescent properties. The stoichiometries depend on the molar ratio and the heterometal. Thus, the reaction with [Cu(NCMe)4]+ in a molar ratio 2:1 gives the trinuclear compounds [Au2CuCl 2(P-N)2]+, in which the structure and Au...Cu interactions depend on the phosphine ligand. With rhodium and iridium derivatives the reactivity is different leading to complexes of the type [AuMCl2(cod)(P-N)] for P-N = PPh2py, PPhpy2, and [Au2M2Cl(cod)2(P-N)2]Cl with PPh2CH2CH2py. Using [MCl2(NCPh) 2] (M = Pd, Pt) in a 2:1 molar ratio yields [Au2MCl 4(P-N)2] and in a 1:1 molar ratio [AuPdCl 3(μ3-PPhpy2)]. Several compounds have been characterized by X-ray diffraction showing in many cases short Au...M distances. The luminescence of these derivatives has been studied. The metalloligands display bands assigned to intraligand (IL) transitions. For the bimetallic (Au/M) systems the luminescence depends on the heterometal present and on the metallophilic interactions. The most important excitations in the relevant energy range were assigned essentially a MMLCT character (from Rh/Ir and Au to ligands) based on density functional theory (DFT) calculations in selected complexes. The luminescence behavior in Rh/Ir [AuMCl 2(cod)(PPh2py)] complexes was interpreted on the basis of the different nature of the half occupied orbitals in the triplet state.
- Calhorda, Maria Jose,Ceamanos, Carmen,Crespo, Olga,Gimeno, M. Concepcion,Laguna, Antonio,Larraz, Carmen,Vaz, Pedro D.,Villacampa, M. Dolores
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p. 8255 - 8269
(2010/12/18)
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- Gold(I) Complexes of P,N ligands and their catalytic activity
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Gold(I) complexes were readily prepared by reaction of the respective ligands with (Me2S)AuCl in CH2Cl2. Complexes of formula LAuCl (L = diphenyl(2-pyridyl)phosphane (PPh2Py), (R)-(+)-4-[(2)-(dlphenylphosphanyl)-1-naphthyl]N-[(R)-1-phenyIethyl] -1-phthalazinamine (PINAP)) were obtained when a 1:1 molar ratio of ligand to starting gold precursor was used. When a 2:1 ratio of ligand to gold precursor was used with PPh2Py or MandyPhos as ligands, complexes of the type L2AuCl were obtained. All complexes were fully characterized, and single-crystal X-ray structures could be determined for four complexes. Chloride ions were removed by reaction with silver salts, such as AgNTf2, AgOTf and AgBF4, for the use of these complexes as catalysts. After the catalytic reaction with alkynes and alcohols in acetonitrile, a unique trinuclear gold(I) complex derived from [(PPh2Py)-Au]BF4 could be characterized by X-ray structural analysis, showing a mode of catalyst deactivation.
- Khin, Chosu,Hashmi, A. Stephen K.,Rominger, Frank
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p. 1063 - 1069
(2010/06/20)
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