Molybdenum oxo-alkoxides

Chisholm and co-workers have shown that reactions involving [Mo2(OR)6] or [Mo(OR)4] c molecules and O2 are affected by the steric effect of the R group and afford a plethora of novel molybdenum oxo-alkoxides (Eq. 5.18). " ... 

The structures of several of these molybdenum oxo-alkoxides have been determined and are discussed in Section 5. 

Alcohol exchange of metal oxo-alkoxides has also been studied. Thus the molybdenum oxo-alkoxides [Mo02(OR>2] (R = Pr, CH2Bu ) were obtained from the tertiary butoxo compound (Eq. 5.30). " ... 

A vanadium(v)-molybdenum(vi) heterometallic oxo-alkoxide [V2Mo2(0)g (0Me)2 (0CH2)3C(CH20H) 2] has also been characterized. The V2M02O16 core involving octahedral metals is reminiscent of the Ti40ie core of titanium tetraUcoxides. ... 

Gibson V.C., Graham A.J., Ormsby D.L., Ward B.P., White A.J.P., WiUiams D.J. The effect of Br0nsted acids on the stability of oxo-alkoxide and imido-alkoxide complexes of molybdenum. J. Chem. Soc., Dalton Trans. 2002 2597... 

Photoelectron spectroscopy (PES) has been shown to provide a convenient probe of metal ion effective nuclear charge and the nature of the metal-ligand bond via the energy of valence-electron photoionizations (16, 20, 22, 284, 285, 312, 332-334). Recently, PES spectroscopy has been employed in the study of oxo-molybdenum compounds of the type (L-A5)MoE(X,Y) [E = O, S, NO X, Y = halide, alkoxide, or thiolate] in order to evaluate the synergy between the axial (E) and equatorial (X,Y) donors in affecting the ionization energy of the HOMO localized on the Mo center (16, 284, 334). These studies have conclusively shown that equatorial dithiolene coordination electronically bulfers the Mo center in (L-A pMoEttdt) (Fig. 13) from the severe electronic perturbations associated with the enormous variation in the Ji-donor/acceptor properties... 

In 1998, the anodic oxidation of molybdenum and tungsten in alcohols in the presence of LiCl (as electroconductive additive) was found to yield a variety of interesting oxo-metal alkoxide complexes, some of which have been authenticated by singlecrystal X-ray crystaUograpy. 

---