39048-41-4Relevant academic research and scientific papers
Oxidation of molybdenum(0) and tungsten(0) carbonyl complexes with silver triflate
Abbott, Andrew P.,Malkov, Andrei V.,Zimmermann, Nicole,Raynor, J. Barrie,Ahmed, Ghafoor,Steele, John,Ko?ovsky, Pavel
, p. 3690 - 3695 (1997)
Benzyltriethylammonium chloropentacarbonylmolybdate (1) and chloropentacarbonyl-tungstate (2) complexes react with CF3SO3Ag in DME via a combination of chloride exchange and a redox process, as revealed by cyclic voltammetry and ESR spectrometry. The resulting intermediate M(I) species disproportionate to M(0) and M(II) so that 3 equiv of TfOAg are required for the quantitative conversion into the M(II) complex. Analogous PPN complexes 3 and 4 only undergo the redox process (in DME); in this instance, the chloride exchange is precluded, presumably due to strong pairing of the complex anion with the counterion.
Chemical and X-ray Structural Stadies on the (Acetato)- and (Trifluoroacetato)pentacarbonylmetalates of Chromium and Molybdenum
Cotton, F. Albert,Darensbourg, D. J.,Kolthammer, B. W. S.
, p. 398 - 405 (2007/10/02)
The reaction of , PNP = +, with AgO2CCH3 and AgO2CCF3 in dichloromethane readily affords the complexes (1) and (2a) in good yield.The trifluoroacetate derivative of chromium (2b) is conveniently prepared in a similar manner.All three compounds crystallize in the triclinic space group (*) with cell dimensions a = 10.563 (1) Angstroem, b = 12.154 (2) Angstroem, c = 17.047 (2) Angstroem, α = 104.01 (1) deg, β = 106.86 (1) deg, γ = 91.79 (1) deg for 1, a = 10.766 (2) Angstroem, b = 12.210 (1) Angstroem, c = 17.115 (2) Angstroem, α = 104.10 (1) deg, β = 106.59 (1) deg, and γ = 92.77 (1) deg for 2a, and a = 10.715 (2) Angstroem, b = 12.141 (2) Angstroem, c = 17.070 (2) Angstroem, α = 104.21 (1) deg, β = 106.57 (1) deg, and γ = 92.56 (2) deg for 2b.The structure of 1 was refined to values of R1 = 0.069 and R2 = 0.083 for 54 atoms (18 anisotropic) and 2860 reflections with I > (*), while 2b was refined to values of R1 = 0.073 and R2 = 0.089 for 57 atoms (21 anisotropic) and 3470 reflections with I > (*).The structure 2a converged with R1 = 0.050 and R2 = 0.070 for 5338 reflections with I > (*) and 57 anisotropic atoms.The most significant structural aspects are essentially equivalent (M)O-C and C=O bond lengths and short trans M-C(O) bond distances.Ligand substitutional processes involving displacement of either the acetate or carbonyl ligands in are very facile, thus making them interesting and useful for preparing other compounds.
