Structures of two molybdenum oxo complexes [MoOCl3(OPPh3)2] and [MoOI(dmpe)2]I

Beth E. Owens (1) , Rinaldo Poli (1)

1 University of Maryland [College Park]

Trichlorooxobis(triphenylphosphine oxide-O)molybdenum(V), [MoOCI3(C18H15OP)2], Mr =774.88, monoclinic, C2/c, a= 14.041 (2), b = 13.126(1), c=19.210(4) Å, β =96.08(1) °, V = 3521 (2) Å3, Z = 4, Dx = 1.46 g cm-3, λ (Cu Kα) = 1.54178 Å, μ = 64.06 cm-I, F(000) = 1572, T = 293 K, R = 0.064 for 2054 observed reflections. The compound was obtained by refluxing [Cp2Mo2Cl5]- and POPh3 in THF. Electron paramagnetic resonance (EPR) spectral parameters (X-band, room temperature, CH2Cl2): g = 1.938, aMo = 54.7 G. The compound adopts an octahedral geometry with cis phosphine oxide ligands and a meridional arrangement of the three Cl atoms. There is disorder between the O and Cl atoms which are related by a crystallographic twofold axis. Bis[1,2-bis(dimethylphosphino) ethane-P,P']iodooxomolybdenum(IV) iodide, [MoOI(C6HI6P2)2]I, Mr = 666.03, monoclinic, P21/n, a = 11.310 (2), b = 15.580 (6), c = 13.741 (3) Å, β = 96.58 (2) °, V= 2405 (2) Å3, Z = 4, Dx = 1.84 g cm-3, λ(Cu Kα) = 1.54178 Å, μ = 276.67 cm-1, F(000) = 1280, T = 296 K, R = 0.056 for 2343 observed reflections. The cation has trans geometry and exhibits a fairly long Mo-I distance of 2.964 (2) Å.

Domaines: Chimie de coordination; Cristallographie

Beth E. Owens, Rinaldo Poli. Structures of two molybdenum oxo complexes [MoOCl3(OPPh3)2] and [MoOI(dmpe)2]I. Acta Crystallographica Section C : Crystal Structure Communications [1968-2013], 1992, 48 (12), pp.2137-2140. ⟨10.1107/S010827019200475X⟩. ⟨hal-03534524⟩