Dinuclear molybdenum, bonding, bridging

Molybdenum dialkyldithiocarbamates Molybdenum dialkyldithiocarbamates are multifunctional lubricant additives as anti-wear, anti-friction and antioxidants. Molybdenum dialkyldithiocarbamates are also multifunctional antioxidants due to the hydroperoxide decomposing ability of dialkyldithiocarbamates, see Section 4.4.2, and the radical scavenging capacity of molybdenum. The best established structure for molybdenum dialkyldithiocarbamates is a six-coordinate complex of a dinuclear molybdenum centre with each molybdenum bonded to terminal oxygen or sulphur atoms, two bridging oxygen or sulphur atoms and one dialkyldithiocar-bamate ligand. Fig. 4.6 [44] ... 

Radius, U. Attner. J. Dinuclear molybdenum(III) and tungsten(III) calix[4]arene complexes — Metal-metal triple 27. bonds supported by bridging calix[4]arene ligands. Eur. J. 

Analysis of the Bonding in Dinuclear Molybdenum Compounds with Bridging Methyl and Hydride Ligands as a Representative Study... 

Table 4 Comparison of calculated bond orders for a series of dinuclear molybdenum compounds with those predicted by two alternative electron-counting methods. In each case, the bond order predicted by the [p.-LX] half-arrow method corresponds exactly to that derived by consideration of the orbital occupations, whereas the half-electron method fails for compounds with bridging hydride and methyl ligands. Data ttiken from reference 6...

Dithiocarbamates, in Ru and Os half-sandwiches, 6, 493 Dithiocarbenes, Pt complexes, 8, 439 Dithiocarboxy ligands, in molybdenum carbonyls, 5, 447 Dithiolate-bridged compounds in dinuclear iron compounds with Fe-Fe bonds, 6, 238 as iron-only hydrogenase biomimetic models, 6, 239 Dithiolate diamides, with Zr(IV), 4, 784 Dithiolene—uranium complexes, synthesis and characterization, 4, 212 Ditopic receptors, characteristics, 12, 489 Ditungsten complexes, associated reactions, 5, 748 Divinyllead diacetates... 

For mononuclear complexes, reactions at coordinated ligands is a topic of major study, and numerous reviews and even books have been written on this topic. At the time of writing this review, the authors could find no major review articles in this area for dinuclear compoimds. The best examples are probably those on the reactions of coordinated molybdenum sulfides discussed earlier. A related observation is the reaction of metal carbonyls with Lewis acids. It has been observed by Shriver and coworkers that carbonyl ligands bridging metal-metal bond atoms show increased tendency to coordinate Lewis acids (equation 96). 

Sulfur dioxide is known to behave as an S—O bidentate to metal ions in low oxidation states, resulting in the formation of three-membered chelate rings. The structures of three such complexes of molybdenum have been described by Kubas and Ryan,including an unusual dinuclear complex in which the SO2 ligands bridge two Mo atoms. A closely related complex of Ru also has been characterized. This bonding form was discussed in relation to these structimes. 

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