Molybdenum with dithiocarbamates, compounds

The reaction between [MoCl4(NCPr)2] and dithiocarboxylic acids is a general route to the preparation of eight-coordinate [Mo(S2CR)4] complexes.168 The crystal structure of [Mo(S2CPh)4] reveals these compounds to be isostructural with the dithiocarbamates, with a dodecahedral coordination around the molybdenum and average Mo—S distances of 2.475(1) and 2.543(1) A to the two different sulfur sites.170 Cyclic voltammetry has shown that in [Mo(acda)4] (Hacda = 2-aminocyclopent-l-ene-l-dithiocarboxylic acid) the Mo can be reversibly oxidized and reversibly reduced in one-electron processes.171... 

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... 

Table 5.15. Protective tribofilm formation from degradation of molybdenum dithiocarbamate (MoDTC), molybdenum dithiophosphate (MoDDP) and molybdenum amine-ester complex (MoAC) directly and in combination with ZDDPs or sulfur compounds...

The (IsQ-coordinated species [Mo(CO)3(py)3] prepared from [Mo(CO)6] and pyridine is useful for the synthesis of various jr-allyl molybdenum compounds (68JOM(13)Pl, 970M5365). The 3-allyl complexes [( 3-allyl)Mo(CO)2Br(py)2] form [( 3-allyl)Mo(CO)2(S,S)(py)] with the anionic S,S-donors, dithiocarbamates and xanthates of sodium and potassium, M (S,S) (81JOM(218)185). [( 3-C3H5)Mo(CO)2(py)2Br] (68JO M(14)375) with thallium hexafluorophosphate in acetonitrile gives... 

Although Mo (II) and W(II) exhibit the most extensive seven-coordinate chemistry yet known (consistent with the application of the effective atomic number rule to these systems), a survey of the substituted metal carbonyl complexes of molybdenum and tungsten reveals no structural data for compounds of the type M(00)3(6-6)2 where 6-6 is a bidentate monoanionic ligand. No tungsten tricarbonyls of this type have been reported to date, but McDonald and co-workers have synthesized and studied the closely related W(CO)2(PPh3) (6-6)2 compounds where 6-6 is a chelating dithiocarbamate (7), xanthate, or dithiophos-phate (8). For molybdenum, the compounds Mo(CO)3(dtc)2(dtc = R2NCS2") (9) are examples of the M(CO)3(6-6)2 type as is Mo(CO)3-[S2P(i-Pr)2]2 (10), which has been well characterized in solution. 

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