Reactivity of molybdenum complexes containing mixed NHNPhR and NNPhR hydrazido ligands (R=Ph, Me) toward di-imines. X-ray crystal structures of [MoO(NNPh 2)Cl 2(bpy)]·CH 2Cl 2, [MoO(NNPh 2)Cl 2(phen)]·CH 2Cl 2 and [Mo(NNPh 2) 2Cl 2(phen)

Abstract

Complexes of the type [Mo(NHNPhR)(NNPhR)(acac)Cl 2] (R=Ph ( I); Me ( II)) react in dichloromethane with the di-imines 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen) to yield, after slow evaporation under air of the solvent, the species [MoO(NNPhR)Cl 2(bpy)] (R=Ph ( III); Me ( IV)) and [MoO(NNPhR)Cl 2(phen)] (R=Ph ( V); Me ( VI)). When these reactions are carried out in toluene under inert atmosphere, I and II give the bis-hydrazido(2−) complexes [Mo(NNPhR) 2Cl 2(bpy)] (R=Ph ( VII); Me ( VIII)) and [Mo(NNPhR) 2Cl 2(phen)] (R=Ph ( IX); Me ( X)). The crystal structures of III, V and IX are reported. Crystals of III are orthorhombic, space group Pbca, with cell parameters a=15.290(6), b=16.225(8), c=19.954(9) Å, Z=8, R=0.036 and R w=0.044. Crystals of V are triclinic, space group P 1 ̄ , with a=8.935(1), b=12.960(2), c=13.443(2) Å, α=61.84(1), β=74.75(1), γ=86.96(1)°, Z=2, R=0.036 and R w=0.044. Crystals of IX are triclinic, space group P 1 ̄ , with a=9.812(4), b=10.459(4), c=17.979(7) Å, α=73.69(3), β=77.98(3), γ=66.30(3)°, Z=2, R=0.038 and R w=0.043. All complexes display similar pseudooctahedral geometries with the hydrazido(2−) ligands adopting the nearly linear coordination mode.