A. Camus

Synthesis of new cationic complexes of rhodium(I)

Abstract New rhodium(I) cationic complexes containing 2,2′-bipyridine and 1,10-phenanthroline in 1 1 metal/chelate rations have been prepared and their reactions studied. Displacement reactions are discussed in terms of the nature of theentering ligands.

Structure determination of the 2:1 derivatives of copper(I) bromide and iodide with bis(diphenylphosphino)methane. A simple structural scheme for the formation of (CuX)nLm species

Abstract The structures of the complexes (CuX)2DPM (X = Br, I; DMP = bis(diphenylphosphino)methane) were determined from three dimensional X-ray data collected by counter methods. The iodine derivative crystallizes in the space group Pbca with eight units in a cell defined by a = 17.128(9), b = 18.306(9) c, = 16.508 (8) A. The structure was refined by the least-squares method to a final R factor of 0.054 for 1336 non-zero independent reflections. The bromine derivative crystallizes in the space group P21/c with eight units in a cell defined by a = 23.707(1), b = 17.805(9), c = 16.991(1) A, β = 136.10(5)°. The final least-squares refinement, based on 2489 non-zero independent reflections, gave an R factor of 0.074. Both the compounds have similar structures with a centrosymmetric (CuX)4 core, in which two copper atoms have a tetrahedral geometry, while the other two are trigonal. The above structures are compared with those already reported for other compounds (CuX)nLm and a single scheme is proposed to rationalize the different geometries of the (CuX)n core on the basis of steric and electronic effects.

Complexes of rhodium(I) and iridium(I) with 2,2′-bipyridine and similar ligands as hydrogenation catalysts

Abstract Complexes of the type [Rh(Chel)ED]PF6 (Chel = 2,2-bipyridine; 1,10-phenanthroline; methyl substituted phenanthrolines; ED = 1,5-hexadiene; X- = PF6-; B(Ph)4) have been synthesized. They are good catalysts for hydrogenation of ketones in an alkaline medium even at atmospheric pressure and room temperature. In the presence of an excess of Chel (Chel : Rh = 2), they also catalyse the selective reduction of C=O groups in the presence of C=C bonds.

Complexes of rhodium(I) with 2,2′-bipyridine and 1,10-phenanthroline : Synthesis and reactions of cationic carbonyl derivatives

The synthesis and reactions of RhI carbonyl complexes of the type [RhChel(CO)2]+ and RhChelCOX (Chel = Bipy, Phen; X = Cl, Br, I) are described. Coordinative, oxidative-addition, and substitution reactions are compared with those of the corresponding IrI derivatives.

Substituted phenylcopper(I) compounds

The reaction of CuBr with methyl- and methoxyphenyllithium derivatives and the isolation of the o-tolyl-, m-tolyl-, p-tolyl- and o-anisylcopper are described. Thermal decomposition, hydrolysis and some other reactions are examined. IR and X-ray powder spectra (including phenylcopper) are reported.

Diolefinic complexes of rhodium(I) and iridium(I) with nitrogen-containing ligands

Abstract The synthesis and the substitution and oxidation reactions of the series of Rh1 and Ir1 complexes M(LL)(B)Cl, [M(LL)(B)2]X and [M(LL)(Chel)]X (LL = cis, cis-cycloocta-1,5-diene, cycloocta-1,3,5,7-tetraene, bicyclo[2.2.1]-hepta-2,5-diene; Chel = 8-aminoquinoline, phenylendiamine, dipyridylketone, substituted phenanthrolines; X = Cl−, PF6−, ClO4−) are described. The use of these complexes as anti-tumour agents is considered.

Phenylcopper complexes with tertiary phosphines and with triphenylborane

Abstract Reactions of phenylcopper with some representative Lewis bases and acides are described. The complexes (CuPh) 2 PPh 3 , (CuPh) 3 PPh 3 , (CuPh) 2 PBu 3 are reported. The IR absorption frequencies of the PPh 3 complexes in the 1600–700 cm −1 region are assigned and discussed. Tetraphenylboroncopper is obtained by addition of CuPh to BPh 3− . The IR spectrum is assigned and compared with those of other tetraphenylborate compounds.

Transfer of hydrogen from alcohols to ketones catalyzed by iridium complexes with 2,2′-bipyridine, 1,10-phenanthroline, and their derivatives

Abstract Complexes of the type Ir(I)chelCODCl (chel = bipy; 4,4′-Me 2 bipy; phen; 4,7-Me 2 phen; 3,4,7,8-Me 4 phen; 4,7-Ph 2 Phen; COD = 1,5-cyclooctadiene) catalyze the hydrogen transfer from alcohols to ketones. The dependence of the rate and the stereoselectivity on the complex, the concentrations of the water and KOH is studied in detail, and a reaction mechanism is proposed. The most active of the above complexes is the 3,4,7,8-Me 4 phen derivative, which gaves turnovers of up to 1150 cycles/min and is still efficient at 4 X 10 −6 M concentration. Furthermore it favours the formation of the trans alcohol in the reduction of the t-butylcyclohexanone with high stereoselectivity.

Selective hydrogenation of unsaturated ketones by rhodium(I) complexes containing 2,2′-bipyridine ligand

Abstract The selective homogeneous reduction of CO groups in the presence of CC bonds with [Rh(Bipy)S 2 ] + or [Rh(Bipy) 2 ] + as catalyst was studied. Stereochemical features of the hydrogenation of substituted cyclohexanones with the two complexes are also reported.

Complexes of iridium(I) with 2,2′-bipyridine and 1,10-phenanthroline: Synthesis and reactions of cationic complexes with diolefins

Abstract The synthesis and reactions of IrI complexes of the type [IrChel(L—L)]+ (Chel = Bipy or Phen; L—L = cyclooctadiene or 2,5-norbornadiene) are described. Coordinative- and oxidative-addition, and substitution reactions are compared with those of the corresponding RhI derivatives.