REDUCTIVE NITROSYLATION OF MOLYBDATE(VI) BY HYDROXYLAMINE IN ALCOHOLIC SOLUTIONS - PREPARATION, SPECTROSCOPIC CHARACTERIZATION AND ELECTRONIC-STRUCTURE OF MONOSYL AND DINITROSYL MOLYBDENUM COMPLEXES - CRYSTAL-STRUCTURE OF [MO(NO)CL(OME)2(PHEN)].MEOH

The reaction of molybdenum(VI) with NH2OH.HCl in (i)PrOH solution leads to the formation of dinitrosyl complexes, whereas that in MeOH leads fundamentally to the mononitrosyl complexes. In these reactions complexes of composition cis-dinitrosyl-trans-dichloro-cis-L2 Mo(NO)2L2Cl2 (L = (i)PrOH, py), {Mo(NO)2(O(i)Pr)2}n and Mo(NO)2Cl(OMe)2L2 (L = MeOH, py; L2 = phen) were isolated. The complexes have been spectroscopically (IR, UV-Vis, H-1 NMR) characterized. The crystal structure of [Mo(NO)Cl(OMe)2(phen)].MeOH was deter-mined by the single-crystal X-ray diffraction method. The compound crystallized in the monoclinic space group P2(1)/m with a = 8.364(3), b = 11.674(4), c = 9.125(3) angstrom, beta = 104.29(3)-degrees and Z = 2. The structure was solved by conventional methods, resulting in a final R factor of 0.028 for 1732 independent reflections. The electronic structure of these mono- and dinitrosyl complexes was recognized by semiquantitative Fenske-Hall LCAO MO calculations. Catalytic activity of these complexes in the olefin metathesis reaction was also examined.