Molybdenum phosphine

Molybdenum(0) also forms a variety of dinitrogen complexes (41), especially when there are phosphine ligands in the molybdenum coordination sphere (see Fig. 7c). This type of complex has been extensively studied because the coordinated dinitrogen is reduced to ammonia upon acidification. 

However, when either P(CgH )(CH2)2 or P(CgH )2(CH2) is used to form cis- or /n j -M(N2)2(PR3)4j M = Mo or W, respectively, followed by treatment with acid, ammonia yields of about 2 mol or 0.7 mol pet mole of complex for M = W and Mo, respectively, are produced (193,194). These and related data have been used to suggest a possible stepwise sequence for the reduction and protonation of N2 on a single molybdenum atom ia nitrogeaase (194). However, acidificatioa leads to complete destmctioa of the complex. Using both the stabilizing effect of the chelating phosphine triphos,... 

Although trialkyl- and triarylbismuthines are much weaker donors than the corresponding phosphoms, arsenic, and antimony compounds, they have nevertheless been employed to a considerable extent as ligands in transition metal complexes. The metals coordinated to the bismuth in these complexes include chromium (72—77), cobalt (78,79), iridium (80), iron (77,81,82), manganese (83,84), molybdenum (72,75—77,85—89), nickel (75,79,90,91), niobium (92), rhodium (93,94), silver (95—97), tungsten (72,75—77,87,89), uranium (98), and vanadium (99). The coordination compounds formed from tertiary bismuthines are less stable than those formed from tertiary phosphines, arsines, or stibines. 

Casares, J.A., Espinet, P., Hernando, R., Iturbe, G., Villafane, F., Ellis, D.D. and Orpen, A.G. (1997) Poly(2-pyridyl) phosphines, PPynPh3 (n = 2, 3), and Their P-Substituted Derivatives as Tripodal Ligands in Molybdenum(O) Carbonyl Complexes. Inorganic Chemistry, 36(1), 44-49. 

NEW DEVELOPMENTS IN SYNTHETIC NITROGEN FIXATION WITH MOLYBDENUM AND TUNGSTEN PHOSPHINE COMPLEXES1 ... 

IV. Molybdenum Dinitrogen Complexes with Polydentate Phosphine... 

Korkisch and Koch [106,107] determined low concentrations of uranium in seawater by extraction and ion exchange in a solvent system containing trioctyl phosphine oxide. Uranium is extracted from the sample solution (adjusted to be 1 M in hydrochloric acid and to contain 0.5% of ascorbic acid) with 0.1 M trioctylphos-phine oxide in ethyl ether. The extract is treated with sufficient 2-methoxyethanol and 12 M hydrochloric acid to make the solvent composition 2-methoxyethanol-0.1 M ethereal trioctylphosphine acid-12 M hydrochloric acid (9 10 1) this solution is applied to a column of Dowex 1-X8 resin (Cl" form). Excess of trioctylphosphine oxide is removed by washing the column with the same solvent mixture. Molybdenum is removed by elution with 2-methoxyethanol-30% aqueous hydrogen peroxide-12 M hydrochloric... 

The formation of rings that contain a thioether linkage does not appear to be catalyzed efficiently by Ru, even when terminal olefins are present. On the other hand, molybdenum appears to work relatively well, as shown in Eqs. 30 [207] and 31 [208]. Under some conditions polymerization (ADMET) to give poly-thioethers is a possible alternative [26]. Aryloxide tungsten catalysts have also been employed successfully to prepare thioether derivatives [107,166,169]. Apparently the mismatch between a hard earlier metal center and a soft sulfur donor is what allows thioethers to be tolerated by molybdenum and tungsten. Similar arguments could be used to explain why cyclometalated aryloxycarbene complexes of tungsten have been successfully employed to prepare a variety of cyclic olefins such as the phosphine shown in Eq. 32 [107,193]. 

S. P. Nolan, C. D. Hoff. The Heats of Reaction of Phosphines with Toluene-Molybdenum Tricarbonyl. Importance of Both Steric and Electronic Factors in Determining the Mo-Plf Bond Strength. J. Organometal. Chem. 1985, 290, 365-373. 

Together with Schrock s molybdenum-imido compound 50 ° the ruthenium-phosphine complexes 51 and especially 52 developed by Grubbs " proved to be an outstanding achievement in the development of molecular catalysts for olefin metathesis reactions (Scheme 10). 

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