119820-44-9Relevant articles and documents
High-yield synthesis of Mo(η6-PhPMe2)(PMe2Ph)3 and its dimerization to form {Mo(μ-η1,η6-PMe2Ph) (PMe2Ph)2}2, a complex characterized by X-ray crystallography
Cotton, F. Albert,Luck, Rudy L.,Morris, Robert H.
, p. 1282 - 1287 (2008/10/08)
The reduction of Mo2Cl10 with Mg in THF in the presence of PMe2Ph at 70°C yields the η6-bonded arylphosphine complex Mo(η6-PhPMe2)(PMe2Ph)3 in high yields. This complex does not undergo substitution reactions with CO and P(OMe)3 at ca. 25°C. A substitution reaction occurs with 1 mol of P(OMe)3 at 45°C to form the monosubstituted derivative Mo(η6-PhPMe2)(PMe2Ph) 2(P(OMe)3). The reaction of Mo(η6-PhPMe2)(PMe2Ph)3 with 1/2[RhCl(COD)]2 (COD = 1,5-cyclooctadiene) initially results in the bimetallic complex Mo(η6-PhP(RhCl(COD)}Me2)(PMe2Ph) 3. The dinuclear complex [Mo(μ-η1, η6-PMe2Ph)(PMe2Ph)2]2 is obtained in the reaction of Mo(η6-PhPMe2)(PMe2Ph)3 and ReH7(PPh3)2. The structural assignments are based on 1H and 31P{1H} NMR spectra, elemental analysis, and in the case of the dimer a single-crystal X-ray structural determination. The cyclic voltammograms for Mo(η6-PhPMe2)(PMe2Ph)3 and some analogues are also reported. The dimer crystallizes in the monoclinic space group P21/c with cell dimensions a = 11.699 (2) A?, b = 12.117 (1) A?, c = 16.352 (2) A?, β= 93.1 (1)°, V = 2314.6 (7) A?3, and Dcalcd = 1.465 g/cm3 for Z = 2. The structure was solved by a three-dimensional Patterson map and refined by least-squares and Fourier methods to final residuals R = 0.031 (Rw = 0.039) for 3299 observed (Fo2 > 3σ(Fo)2) reflections. The geometry about the molybdenum is distorted octahedral. Averaged principal bond lengths are Mo-C(ring) = 2.27 [1] and Mo-P = 2.433 [2] A?, and the Mo-Mo distance is 4.9706 (3) A?.
