24554-64-1Relevant academic research and scientific papers
Thermal reaction of Mo2I4(CO)8 with PMe2Ph, PEt2Ph, and pyridine. Formation of metal-metal quadruple bonds vs. disproportionation. X-ray crystal structures of MoI3(PMe2Ph)2(POMe2Ph) and [PHEt2Ph][MoI4(PEt2Ph)2]
Cotton, F. Albert,Poli, Rinaldo
, p. 3624 - 3629 (2008/10/08)
The thermal reactions of Mo2I4(CO)8 with PMe2Ph, PEt2Ph, and pyridine (py) have been studied. The reaction with pyridine leads to disproportionation with formation of Mo(CO)3(py)3 and MoI3(py)3. The reactions with the two phosphines in toluene as solvent lead to disproportionation as well as to the formation of the Mo2I4L4 (L = PMe2Ph, PEt2Ph) dimers with metal-metal quadruple bonds. The use of THF as solvent in the PEt2Ph reaction suppresses the formation of the molybdenum(II) dimer in favor of disproportionation. Compounds Mo2I4(PMe2Ph)4 (1) and MoI3(PMe2Ph)2(POMe2Ph) (2) have been isolated from the PMe2Ph reaction in toluene, while the compound [PHEt2Ph][MoI4(PEt2Ph)2] (3) has been obtained from the PEt2Ph reaction in THF. Compounds 2 and 3 have been structually characterized by X-ray diffraction methods. Compound 2: space group Pmn21, a = 13.801 (3) ?, b = 12.303 (3) ?, c = 9.298 (1) ?, V = 1578.7 (8) ?3, Z = 2, R = 0.0516 (Rw = 0.0622) for 1038 data with Fo2 > 3σ(Fo2). Compound 3: space group P21/c, a = 20.144 (6) ?, b = 10.368 (2) ?, c = 19.822 (3) ?, β = 109.37°, V = 3904 (3) ?3, Z = 4, R = 0.0371 (Rw = 0.0540) for 3902 data with Fo2 > 3σ(Fo2). A possible mechanism that interrelates the two different pathways is discussed.
Consecutive Substitution in, and Reduction of, η-Allyl Molybdenium(II) Complexes, and a Study of Ligand Exchange in a Molybdenium(0) Product
Clark, Deborah A.,Jones, David L.,Mawby, Roger J.
, p. 565 - 569 (2007/10/02)
Reactions of the allyl and 2-methylallyl complexes (R=H or Me) with ligands L=PMe2Ph or PMePh2 involve initial substitution to give followed by reduction to cis- or .The reduction, which is first order in the concentrations of both molybdenium complex and L, is thought to involve initial nucleophilic attack on the allyl ligand.Two of the PMe2Ph ligands in cis-, believed to be the mutually cis pair, undergo rapid dissociative exchange with free PMe2Ph in solution at high temperatures: the exchange occurs without scrambling the cis pair of ligands with the trans pair.In the absence of free PMe2Ph, slow decomposition at 353 K yields specifically the mer isomer of .It is shown that this is the expected result if the labile Mo-P bonds are those to the cis pair of PMe2Ph ligands.
