26500-10-7Relevant academic research and scientific papers
PYRAZOLATE THIOCARBONYLRHODIUM COMPLEXES. X-RAY STRUCTURE OF 2
Uson, R.,Oro, L. A.,Ciriano, M. A.,Carmona, D.,Tiripiccio, A.,Camellini, M.
, p. 69 - 80 (2007/10/02)
The preparation and properties of complexes of general formulae ClO4 (HL=pyrazole (HPz), 3-methylpyrazole (H3-MePz), 3,5-dimethylpyrazole (H3,5-Me2Pz), PR3=triphenylphosphine, tricyclohexylphosphine) and ClO4 are reported.Complexes of the first set react with potassium hydroxide to give 2 or RhPz(CS)(PR3)2 complexes.The structure of the complexes 2 has been determined by X-ray diffraction methods.The crystals are monoclinic, space group P21/c, with Z=4 in a unit cell of dimensions a=12.700(11), b=17.217(16), c=23.041(18) Angstroem, β=116.55(8)o.The structure has been solved by Patterson and Fourier methods and refined by full-matrix least-squares to R=0.059 for 1978 independent reflections.The structure consists of dimeric complexes, in which each rhodium atom is in a square-planar environment being bonded to a carbon atom of a thiocarbonyl ligand, a phosphorus atom of a triphenylphosphine molecule and to two nitrogen atoms of pyrazolate ligands bridging the metal atoms.The dihedral angle of 71.1o between such two square planes leads to a bent configuration with an intramolecular rhodium-rhodium distance of 3.220 Angstroem.The thiocarbonyl and triphenylphosphine ligands are in a trans disposition.
THE CHEMISTRY OF HETERO-ALLENE AND -ALLYLIC DERIVATIVES WITH RHODIUM I. THE REACTIONS OF RHODIUM(I)-HETERO-ALLYLIC COMPOUNDS WITH HETERO-ALLENES; B. CARBON DISULFIDE
Thewissen, D. H. M. W.
, p. 211 - 222 (2007/10/02)
The rhodium(I) complexes Rh(PPh3)2, in which represents an uninegative unsaturated heteroallylic bidentate ligand, coordinating via two of the three heteroatoms (X, Y, Z = P, S or N), react at elevated temperature with an excess of the hetero-allene S=C=S to give the rhodium(I)thiocarbonyl complexes Rh(CS)IPPh3).In the initial step a first CS2 molecule is coordinated side-on by one of the C=S double bands.Subsequent reactions can be blocked at this stage by addition of pyridine, resulting in RhCl(η2-CS2)(PPh3)(py)2.The formation of the CS complexes occurs in two ways.Either by direct sulfur abstraction from the RhI(η2-CS2) complex by PPh3 or by a dimerisation of two CS2 molecules and elimination of a CS moiety, resulting in a RhIII-thiocarbonyl-trithiocarbonato complex, immediately followed by demolition of the trithiocarbonato-CS32- fragment by PPh3 to SPPh3 and CS2.Complexes containing a CS32- fragment, but no CS moiety, can also be identified by IR measurements.These products may be formed in a sidereaction upon elimination of CS.
