Synthetic pathways in binuclear molybdenum chemistry: µ-acetato-, chloro-, and tertiary phosphine derivatives; X-ray structure determination of trans-[{MoCl(PBun3)(µ-O2CMe)}2]

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Abstract
The reaction between [{Mo(µ-OCOMe)2}2] and SiMe3Cl in the presence of a variety of donor ligands L [tetrahydrofuran (thf), Me2S, Et2S, PEt3, PPh3, PBun 3, or Ph2P(CH2)nPPh2, where n= 1 or 2] yields binuclear compounds such as [{MoLCl(µ-OCOMe)}2] or [(MoL2Cl2)2]. The products may vary according to the stoicheiometry of the reaction. The new compounds described are [{MoCl(µ-OCOMe)(thf)}2], [{MoCl2(PPh3)(µ-OCOMe)}2], isomers of [{MoCl(PEt3)(µ-OCOMe)}2], trans-[{MoCL(PBun 3)(µ-OCOMe)}2], and [Mo2Cl2(OCOMe)2(dppm)]. Interconversion of some of these compounds by ligand-replacement reactions is also demonstrated. The crystal structure of trans-[{MoCl(PBun 3)(µ-OCOMe)}2] is described; the crystals are monoclinic, space group P21/n, with a= 14.969(2), b= 15.146(2), c= 8.920(2)Å, β= 105.14(1)°, and Z= 2. Refinement converged with R= 0.048, R′= 0.063, for 1 762 observed reflections [l > 3σ(l)]. The Mo–Mo separation is 2.099(1)Å. The presence of isomers of the various compounds is demonstrated from the hydrogen-1 n.m.r. spectra.