Metallophthalocyanines as catalysts in electrochemical reactions

Reactions of transition metal-coordinated nitriles

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Metal-Assisted Cycloaddition Reactions in Organotransition Metal Chemistry

A spectroscopic and structural investigation of binuclear silver(I) complexes supported by aliphatic phosphine ligands, namely [Ag(PCy3)(O2CCF3)]2 (1), [Ag2(μ-dcpm)2]X2 (X = CF3SO3, 2; PF6, 3; dcpm = bis(dicyclohexylphosphino)methane), and [Ag2(μ-dcpm)(μ-O2CCF3)2] (4), is described. X-ray structural analyses of 1−4 reveal Ag−Ag separations of 3.095(1), 2.948 (av), 2.923 (av), and 2.8892(9) A, respectively. Due to the optical transparency of the phosphine ligands, the UV−vis absorption band at 261 nm in CH3CN for 2 and 3 is assigned to a 4dσ* → 5pσ transition originating from Ag(I)−Ag(I) interactions. The argentophilic nature of this band is verified by the resonance Raman spectrum of 2 with 273.9 nm excitation, where virtually all of the Raman intensity appears in the Ag−Ag stretch fundamental (80 cm-1) and overtone bands. Complexes 2 and 3 exhibit photoluminescence in the solid state at room temperature.

Spectroscopic evidence for argentophilicity in structurally characterized luminescent binuclear silver(I) complexes

Coordination and organometallic chemistry of metal-NO complexes.

Ligand transfer reactions between different metallic sites. Crystal structure of [(C5H5)2Co4(CO)5(F3CCCCF3)]

The study of the far infrared spectral region permits one to distinguish between the pseudo-tetrahedral complexes NiI2L2 (L = R1R2C3S3 where R1 = CH3 and R2 = H, R1 = R2 = CH3, R1 = C4H3S and R2 = H) and the square planar complex NiI2L′2 (L′ = R1R2C3S3 where R1 = C6H5 and R2 = H). The electronic spectra recorded in the solid state confirm the distinction. The displacement of the band νC=S of the molecule 1,2-dithio-1-3-thione which enters the sphere of coordination is more marked in the complexes of cobalt(II) than in the corresponding nickel(II) complexes.

Composés de coordination de molécules soufrées. II. Complexes pseudo-tétraédriques et plan du nickel(II) avec quelques dithiole-1,2 thiones-3

Cyclopendtadienyl vanadium complexes: Di-μ-methylsulfide-bis(dicarbonylcyclopendtadienylvanadium)

The structure of the title compound has been determined by the heavy-atom method from 1 350 reflections, measured with a diffractometer, and refined by full-matrix least-squares methods to R 0.046. Crystal are orthorhombic, space group Pbca, with a= 11.15(2), b= 26.25(4), and c= 7.56(1)A. In the structure the monomeric anions have a pentagonal-bipyramidal co-ordination, with the bidentate peroxo-group and terdentate pyridine-2,6-di-carboxylate group filling the equatorial positions, and the oxide and fluoride ligands in the axial positions. There is a very long MO–F distance (2.058 A), which can be correlated with the trans effect of the oxide ligand (MO–O 1.661 A).

Fluoride crystal structures. Part 31. Ammonium fluoro-oxoperoxo-(pyridine-2,6-dicarboxylato)molybdate(VI)

Resume Des oxochloro(dicetonato)niobates(V) ont ete isoles avec le cation tetraethylammonium. Leur formule generale est {(C 2 H 5 ) 4 N} {NbOCl 3 - (R-CO-CH-CO-R′)}. A l'aide de diverses methodes physiques on propose la stereochimie de l'anion a l'etat solide et en solution. Pour les β-dicetones symetriques ( R = R ′ = CF 3 et R = R ′ = CH 3 ) a l'aide des spectres de RMN on met en evidence la non equivalence des deux groupements CH 3 ou CF 3 , confirmant ainsi l'effet “trans” de la liaison multiple (NbO).

Jacques E. Guerchais

Papers

Ligand transfer reactions between different metallic sites. Crystal structure of [(C5H5)2Co4(CO)5(F3CCCCF3)]

Composés de coordination de molécules soufrées. II. Complexes pseudo-tétraédriques et plan du nickel(II) avec quelques dithiole-1,2 thiones-3

Cyclopendtadienyl vanadium complexes: Di-μ-methylsulfide-bis(dicarbonylcyclopendtadienylvanadium)

Fluoride crystal structures. Part 31. Ammonium fluoro-oxoperoxo-(pyridine-2,6-dicarboxylato)molybdate(VI)

Contribution a l'etude stereochimique d'oxochloro-(dicetonato)niobates(v)