ORGANOTRANSITION-METAL COMPLEXES OF MULTIDENTATE LIGANDS .17. SYNTHESIS AND CHARACTERIZATION OF SOME ETA-3-ALLYLCARBONYL COMPLEXES OF MOLYBDENUM CONTAINING DITHIOCARBAMATES AS THE UNI-NEGATIVE SULFUR-BIDENTATE LIGANDS - CRYSTAL-STRUCTURE OF [MO(ETA-2-S2CNET2)(CO)-(ETA-3-ALLYL)(ETA-2-BIS(DIPHENYLPHOSPHINO)METHANE)]

Complexes with a general formula of [Mo{eta-2-(S,S)}(CO)2(eta-3-allyl)] ((S,S)- = N,N-diethyldithiocarbamato or pyrrolidine-1-carbodithioato) have been prepared by one of three preparative routes: (1) reaction of the anion, [Mo{eta-2-(S,S)}(CO)4]- with allyl bromide; (2) reaction of [Mo(eta-2-H2CPz'2)(CO)2(eta-3-allyl)Br] (Pz' = 3,5-dimethylpyrazol-1-yl) with (S,S)-; and (3) the substitution reaction between [Mo(MeCN)2(CO)2(eta-3-allyl)Br] and (S,S)-. The complexes are probably mononuclear and diamagnetic, based on the relevant spectral data. These complexes can react with pyridine to give [Mo{eta-2-(S,S)}(CO)2(eta-3-allyl)(py)] and with the phosphorus-bidentate ligand (P,P) to afford [Mo{eta-2-(S,S)}(CO)(eta-3-allyl){eta-2-(P,P)}] ((P,P) = bis(diphenylphosphino)methane (DPPM) or 1,2-bis(diphenylphosphino)ethane (DPPE)), which can also be prepared from the reaction of [Mo{eta-2-(P,P)}(CO)2(eta-3-allyl)Br] with (S,S)-. The new complexes were characterized by element analysis, IR and NMR spectroscopy. The crystal structure of [Mo(eta-2-S2CNEt2)(CO)(eta-3-allyl)(eta-2-DPPM)] was determined to confirm the di-hapticity of (S,S)- and of (P,P) in [Mo{eta-2-(S,S)}(CO)(eta-3-allyl){eta-2-(P,P)}]: space group P2(1)/c, a = 16.028(4), b = 8.867(2), c = 23.459(4) angstrom, beta = 93.12(2)-degrees, V = 3329.1(13) angstrom 3, Z = 4, D(calc) = 1.392 g/cm3, R = 0.067 and R(w) = 0.076 on 3992 reflections with I > 3.0 sigma(I).