14243-66-4Relevant academic research and scientific papers
Structure of Trichloro(triphenylphosphine)gold(III), >
Staples, Richard J.,Grant, Tiffany,Fackler, John P.,Elduque, Anabel
, p. 39 - 40 (1994)
The structure of the title compound displays the same trans effects and slight distortions from planarity as previously reported trihalide(trialkylphosphine)gold(III) structures.
Oxidant speciation and anionic ligand effects in the gold-catalyzed oxidative coupling of arenes and alkynes
Hofer, Manuel,De Haro, Teresa,Gómez-Bengoa, Enrique,Genoux, Alexandre,Nevado, Cristina
, p. 8411 - 8420 (2019/09/30)
The mechanism of the gold-catalyzed oxidative cross-coupling of arenes and alkynes has been studied in detail combining stoichiometric experiments with putative reaction intermediates and DFT calculations. Our data suggest that ligand exchange between the alkyne, the Au(i)-catalyst and the hypervalent iodine reagent is responsible for the formation of both an Au(i)-acetylide complex and a more reactive "non-symmetric" I(iii) oxidant responsible for the crucial Au(i)/Au(iii) turnover. Further, the reactivity of the in situ generated Au(iii)-acetylide complex is governed by the nature of the anionic ligands transferred by the I(iii) oxidant: while halogen ligands remain unreactive, acetato ligands are efficiently displaced by the arene to yield the observed Csp2-Csp cross-coupling products through an irreversible reductive elimination step. Finally, the nature of competitive processes and catalyst deactivation pathways has also been unraveled. This detailed investigation provides insights not only on the specific features of the species involved in oxidative gold-catalyzed cross couplings but also highlights the importance of both ancillary and anionic ligands in the reactivity of the key Au(iii) intermediates.
CuII and AuIII Complexes with Glycoconjugated Dithiocarbamato Ligands for Potential Applications in Targeted Chemotherapy
Pettenuzzo, Nicolò,Brustolin, Leonardo,Coltri, Elisa,Gambalunga, Alberto,Chiara, Federica,Trevisan, Andrea,Biondi, Barbara,Nardon, Chiara,Fregona, Dolores
, p. 1162 - 1172 (2019/05/27)
This work is focused on the synthesis, characterization, and preliminary biological evaluation of bio-conjugated AuIII and CuII complexes with the aim of overcoming the well-known side effects of chemotherapy by improving the selective accumulation of an anticancer metal payload in malignant cells. For this purpose, carbohydrates were chosen as targeting agents, exploiting the Warburg effect that accounts for the overexpression of glucose-transporter proteins (in particular GLUTs) in the phospholipid bilayer of most neoplastic cells. We linked the dithiocarbamato moiety to the C1 position of three different monosaccharides: d-glucose, d-galactose, and d-mannose. Altogether, six complexes with a 1:2 metal-to-ligand stoichiometry were synthesized and in vitro tested as anticancer agents. One of them showed high cytotoxic activity toward the HCT116 colorectal human carcinoma cell line, paving the way to future in vivo studies aimed at evaluating the role of carbohydrates in the selective delivery of whole molecules into cancerous cells.
Halogen photoreductive elimination from gold(III) centers
Teets, Thomas S.,Nocera, Daniel G.
, p. 7411 - 7420 (2009/10/17)
Monomeric complexes of the type Au III (PR 3 )X 3 and bimetallic complexes of the type Au 2 I,III [μCH 2 (R 2 P) 2 ]X 4 and Au 2 III,III [μ-CH 2 (R 2 P) 2 ]X 6 (R = Ph, Cy, X = Cl - , Br - ) undergo facile photoelimination of halogen. M-X bond activation and halogen elimination is achieved upon LMCT excitation of solutions of Au III complexes in the presence of olefin chemical traps. As opposed to the typical one-electron redox transformations of LMCT photochemistry, the LMCT photochemistry of the Au III centers allows for theunprecedented (i) two-electron photoelimination of X 2 from a monomeric center and (ii) four-electron photoelimination of X 2 from a bimetalllic center. The quantum yields for X 2 photoproduction, in general, are between 10percent and 20percent for all species, showing only minimal dependence on the identity of the ligands about gold, or the nuclearity of the complex. Efficient X 2 photoelimination is observed in the absence of a chemical trap, providing a rare example of authentic, trap-free halogen elimination from a transitionmetal center.
Organometallic gold(III) compounds as catalysts for the addition of water and methanol to terminal alkynes
Casado, Raquel,Contel, Maria,Laguna, Mariano,Romero, Pilar,Sanz, Sergio
, p. 11925 - 11935 (2007/10/03)
Different inorganic and organometallic gold(III) and gold(I) complexes have been tested in the addition of water and methanol to terminal alkynes. Anionic and neutral organometallic gold(III) compounds can efficiently mediate these reactions in neutral media in refluxing methanol. The compounds are added in catalytic amounts (1.6-4.5 mol% with respect to the alkyne), Thus, compounds of the general formula Q[AuRCl3], Q[AuR2Cl2], [AuRCl2]2, and [AuR2Cl]2, (Q = BzPPh3+, PPN: N(PPh3)2+ or N(Bu)4+; R = C6F5 or 2,4,6-(CH3)3C6H2) seem to behave as Lewis acids in nucleophilic additions to triple bonds. Some intermediates could be detected in the stoichiometric reaction between [Au(C6F 5)2Cl]2 and phenylacetylene that was followed by variable temperature 1H, 19F{1H}, COSY 19F{1H}-19F{1H}, and 2H{1H} NMR experiments. Compound [Au(C6F 5)2Cl]2 is also able to catalyze the hydration of phenylacetylene at room temperature. A plausible mechanism for the hydration reaction has been proposed.
