Molybdenum xanthates

More recendy, molecular molybdenum-sulfur complexes and clusters have been used as soluble precursors for M0S2 in the formulation of lubricating oils for a variety of appHcations (70). Presumably, the oil-soluble molybdenum—sulfur-containing precursors decompose under shear, pressure, or temperature stress at the wear surface to give beneficial coatings. In several cases it has been shown that the soluble precursors are trifunctional in that they not only display antifriction properties, but have antiwear and antioxidant characteristics as weU. In most cases, the ligands for the Mo are of the 1,1-dithiolate type, including dithiocarbamates, dithiophosphates, and xanthates (55,71). 

The structure of (88) is remarkable two of the xanthato ligands are bonded in a normal, terminal way whereas the other two ligands are terminally bonded to one molybdenum and tf bonded to the other other molybdenum atom as in (89)." The latter bonding type shows that a xanthate can act like an allyl ion. 

This section describes the structural chemistry of 14 molecular structures, 3 of chromium, 8 of molybdenum, and 3 of tungsten. The only binary xanthate structures are those of chromium, all other structures are at least ternary in nature. For the chromium and tungsten structures, conventional monodent-ate and bidentate coordination modes of the xanthate ligand are found. By contrast, a rich, diverse, and fascinating coordination range is observed for the... 

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... 

The rate increase for the isopropyl derivative with respect to the unsubstituted derivative is about 50 times. Steric hindrance prevented the 2,4,6-trisubstituted isopropyl complex from undergoing CO insertion. The acetyl derivatives of molybdenum (II) xanthate, Mo(>j -COMe)(CO)(PMe3)2(S2COR), undergo an equilibrium between the -acyl and another form of the acyl that has been assumed to involve an agostic interaction with the methyl group ... 

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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