24554-82-3

Upstream product

• 24554-64-1 fac-Mo(CO)3(PPhMe₂)3 
• 22547-54-2 2Mo⁽²⁺⁾*4I^(1-)*8CO=Mo₂I₄(CO)8 
• 672-66-2 Dimethyl(phenyl)phosphine 

Downstream Products

• 88326-31-2 mer-[Mo(CO)3(PMe₂Ph)3]⁽¹⁺⁾ 

Relevant academic research and scientific papers

Relative hemilabilities of H2B(az)2 (az = pyrazolyl, dimethylpyrazolyl, methimazolyl) chelates in the complexes [M(η-C3H5)(CO)2{H2B(az)2}] (M = Mo, W)

The reactions of [M(η3-C3H5)Br(CO)2(NCMe)2] (M = Mo, W) or [Mo(η3-C3H5)Br(CO)2(PMe2Ph)2] with Na[H2B(mt)2] (mt = methimazolyl) affords the complexes [M(η3-C3H5)(CO)2{κ3-H,S,S′-H2B(mt)2}], the 3-centre, 2-electron B-H-M interaction of which was found to be inert with respect to opening under mild conditions, while more forcing conditions (heating with PMe2Ph) resulted in cleavage of the entire allyl and borate ligands to form [Mo(CO)3(PMe2Ph)3]. In contrast, the reaction of [Mo(η3-C3H5)Br(CO)2(NCMe)2] with Na[H2B(pz)2] affords either [Mo(η3-C3H5)(CO)2{κ3-H,N,N′-H2B(pz)2}] or (more likely) [Mo(η3-C3H5)(CO)2(NCMe){κ2-N,N′-H2B(pz)2}] which in turn reacts with phosphines to provide [[Mo(η3-C3H5)(CO)2(PPhR2){κ2-N,N′-H2B(pz)2}] (R = Me, Ph). The reactions discussed indicate the propensity for 3-centre, 2-electron B-H-Mo interactions increases in the order H2B(pz)2 2B(pz?)2 2B(mt)2 (pz? = 3,5-dimethypyrazolyl).

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]

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.

Study of substituent effects, isomerization and cross redox reactions associated with electrochemical oxidation of Mo(CO)3P3 systems

Homogeneous and heterogeneous aspects of the redox couple [Mo(CO)3P3]+/0 (P = monodentate phosphorus ligand) have been examined by polarographic, voltammetric, and spectroscopic methods in dichloromethane solution. The tricarbonyl compounds in each oxidation state can exist in both facial (fac+, fac0) and meridional (mer+, mer0) forms. The cyclic voltammograms at room temperature often showed the form of quasi-reversible couples; however, they did not fit theoretical models for simple electron transfer. With use of low temperatures and a variety of scan rates, it was deduced that the electrode processes could be explained in terms of parts of the square reaction scheme fac0 ? fac+ + e- (upward harpoon with barb leftwards) + ? (upward harpoon with barb leftwards) + ? mer0 ? mer+ + e- and the cross redox reaction. fac+ + mer0 ?κ fac0 + mer+ At low temperatures it was possible to calculate E°(fac+/0) and E°(mer+/0) and hence calculate the equilibrium constant, K, for the cross redox reaction. Both K and the E° values showed a very large dependence on the nature of the phosphorus ligand. For fac-Mo(CO)3P3, a satisfactory linear correlation between carbon-13 NMR chemical shift (δ(13C)) of the carbonyl ligands and E°(fac+/0) was obtained, but similar correlations were not observed between E°(fac+/0) and either δ(31P) of the phosphorus ligands or δ(95Mo) of the central molybdenum atom.

Consecutive Substitution in, and Reduction of, η-Allyl Molybdenium(II) Complexes, and a Study of Ligand Exchange in a Molybdenium(0) Product

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.