24169-93-5Relevant academic research and scientific papers
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.
C(3) aurated 1,4-benzodiazepin-2-ones. Synthesis and characterization. Crystal structure of (L)Au[P(C6H4CH3-4)3] (HL=7-chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one, DIAZEPAM)
Minghetti, Giovanni,Zucca, Antonio,Cinellu, Maria Agostina,Stoccoro, Sergio,Manassero, Mario,Sansoni, Mirella
, p. 405 - 415 (2007/10/03)
The synthesis of a series of gold(I) metallated derivatives of some 1,4-benzodiazepin-2-ones is described. They include mononuclear (L)Au(PR3) (R=C6H5, C6H4CH3-4 or C2H5) as well as dinuclear species (L)Au(Ph2P(CH2)nPPh2)Au(L), n=2, 3 (HL=7-chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one, DIAZEPAM or 7-chloro-1-(cyclopropylmethyl)-1,3-dihydro-5-phenyl-2H-1,4-benzodiazepin-2-one, PRAZEPAM). The deprotonated ligand is bonded to the AuPR3 moiety through the C(3) atom. Activation of the C(sp3)-H bond is achieved by means of a strong base in the presence of the phosphinegold chloride intermediate. The structure of (L)Au[P(C6H5CH3-4)3] has been determined by X-ray diffraction. Some aspects of the reactivity of the metallated species is also reported.
