72476-68-7Relevant articles and documents
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.
Governing the oxidative addition of iodine to gold(I) complexes by ligand tuning
Schneider, Daniel,Schier, Annette,Schmidbaur, Hubert
, p. 1995 - 2005 (2007/10/03)
The impact of addition of iodine to gold compounds which is strongly ligand-dependent and indicate a threshold in the oxidation potentials was investigated. A large series of tertiary phosphines were used as ligands for the oxidative addition of iodine. The reactions were followed by 31P NMR spectroscopy and the products crystallized from dichromethane-pentane solutions. Complexes with small triakylphosphines were readily oxidized, while those with more bulky ligands were not. No oxidation took place when the ligands were taken from the triaryphosphine series.
Bidentate Ligand Transfer Reactions between Gold(I) Complexes
Bardaji, Manuel,Laguna, Antonio,Laguna, Mariano
, p. 1255 - 1258 (2007/10/02)
Reactions of the cationic derivative 2 with (1-) (X = Cl or Br) in a 1:1 or a 1:2 molar ratio afforded tri- or di-nuclear derivatives, respectively.Neutral complexes or n(μ-L-L)n> react with the cationic 2>ClO4 in 1:2 molar ratio, to give open-ring complexes ClO4.Reactions of the neutral complexes (R = Me or CH2Ph) with cationic 2 (P-P = Ph2PCH2PPh2 or Ph2PCH2CH2PPh2) led to the heterobridged dinuclear complexes ClO4.All these processes proceed via donor-acceptor intermediates, with bidentate ligand transfer.
Novel ring compounds of bidentate phosphines with gold(I). Two-, three-, and four-co-ordination
Al-Baker, Salam,Hill, William E.,McAuliffe, Charles A.
, p. 2655 - 2660 (2007/10/02)
With n-butylphenylphosphine and gold(I), salts n)x> (x = 1 or 2) and n)x>+ (x = 2,3, or 4) are formed in solution and in the solid state.A range of short-chain and long-chain diphosphines (L), Ph2P(CH2)nPPh2 (n = 1,2,4,6,8,10 or 12) have been employed to prepare the neutral complexes, (x = 1 or 2), in which the gold is two-, and three-co-ordinate, respectively, and the cationic compounds 2 (x = 2,3, or 4) in which the gold is two-, three-, and four-co-ordinate.However, it was only possible to isolate the novel 2 complexes with the short-chain diphosphines, Ph2P(CH2)nPPh2 (n = 2,3, or 4).A 31P-1H> n.m.r. study employing Ph2P(CH2)6PPh2 and AuBr2- at different rations in CD2Cl2 shows the presence of two-, three-, and four-co-ordinate gold, and these species exchange with one another at temperatures > -50 deg C.A similar study at -90 deg C with the other diphosphines gave similar results, except that three- and four-co-ordination exist in the case of the short-chain ligands Ph2P(CH2)nPPh2 (n = 1 or 2) even at very low ligand:gold ratios.
