Molybdenum compounds bonding

Divalent molybdenum compounds occur in mononuclear, dinuclear, and hexanuclear forms. Selected examples are shown in Figure 6. The mononuclear compounds are mostiy in the realm of organometaUic chemistry (30—32). Seven-coordinate complexes are common and include MoX2(CO)2(PR3)2, where X = Cl, Br, and I, and R = alkyl MoCl2(P(CH3)3)4, heptakis(isonitrile) complexes of the form Mo(CNR) 2 (Fig. 6d), and their chloro-substituted derivatives, eg, Mo(CNR)3CR. The latter undergo reductive coupling to form C—C bonds in the molybdenum coordination sphere (33). 

Extended Hiickel molecular-orbital (EHMO) calculations using structural parameters from the X-ray determination of Cp(CO)3Mo 3In (Fig. 29) and ideal symmetry Cih were carried out for this compound in order to investigate the extent of the indium-molybdenum ir-bonding.122 The HOMO of the compound is the 3e molecular orbital, which is In—Mo [Pg.54]

Compounds 4-7 (Table 1) belong to this group. The physicochemical properties of the given binuclear clusters are close to those of the analogous rhenium and molybdenum compounds with the quadruple M-M bonds and are as a rule isostructural with them [1,89,90]. 

Metal-metal bonding, in molybdenum compounds, 17 29-31 Metal-modified glass-ionomer dental cements, 8 283... 

M.H. Chisholm, J.F. Coming, J.C. Huffman, The molybdenum-molybdenum triple bond. 14. Preparation and characterization of mixed alkoxy-thiolate compounds of formula Mo2(OR)2(SAr)4. Inorg. Chem. 23, 754-757 (1984)... 

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... 

RHENIUM AND MOLYBDENUM COMPOUNDS CONTAINING QUADRUPLE BONDS... 

Rhenium, Molybdenum Compounds Containing Quadruple Bonds 83... 

---