Dimolybdenum(II) Bromide Complexes Containing Bidentate Tertiary Phosphine and Arsine Ligands: Kinetic vs. Thermodynamic Reaction Control and Structural Characterization of a Mononuclear Complex Resulting from M-M Bond Cleavage
Derringer, Daniel R.
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The reactions of (NH4)4Mo2Br8 with bidentate tertiary phosphine and arsine donors Ph2P(CH2)PPh2 (dppm), Ph2P(CH2)2PPh2 (dppe), Ph2P(CH2)2AsPh2 (arphos), Ph2P(CH2)3PPh2 (dppp) in refluxing alcoholic solvents MeOH, EtOH and I-PrOH are described. α and ß forms of the products with the general formula Mo2Br4(LL)2 are discussed. Low frequency infrared spectra (400 cm-I - 200 em-I) and electronic absorption data suggest that Mo2Br4(dppm)2' ß-Mo2Br4 (dppe}2 and ß-Mo2Br4(dppp)2 are structurally similar to Mo2Br4(arphos)2 which has been shown to possess bridging arphos molecules. Available evidence suggests that α-Mo2Br4(dppe)2 possesses chelating dppe molecules and forms as the kinetic product which can be converted to the thermodynamic ß-product in solutions of I-PrOH and deoxygenated dichloromethane. Solvent dependence in reaction product distribution is investigated, and the crystal structure of trans-MoBr2(dppe)2, a mononuclear complex resulting from M-M bond cleavage, is reported.
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