Reactions of molybdenum oxo-complexes with substituted hydrazines. Part 2. The reactions of molybdenum(IV) oxo-complexes with aroylhydrazines and the crystal and molecular structure of (N-benzoyldiazene-N′O)[N-benzoyldiazenido(1–)-N′]chlorobis(dimethylphenylphosphine)molybdenum

Abstract

The aroylhydrazines RCONHNH₂(R = Ph, p-ClC₆H₄, p-NO₂C₆H₄, m-NO₂C₆H₄, or 1-C₁₀H₇) react with [MoOCl₂(PR′₃)₃](PR′₃= PMe₂Ph, PEt₂Ph, PPrⁿ₂Ph, PMePh₂, or PEt₃) to give red complexes [MoCl(N₂COR)(NHNCOR)(PR′₃)₂]. Crystals of the title complex with R = Ph and PR′₃= PMe₂Ph are triclinic with a= 8.710, b= 23.000, c= 16.370 Å, α= 97.43, β= 89.21, γ= 101.33°, space group P, and Z= 4. The structure has been solved by Patterson and Fourier methods, and refined, using 3 939 independent reflections, to R 0.098. It is composed of two crystallographically independent monomeric molecules, both having distorted octahedral co-ordination. They are considered to be chemically equivalent, each containing a unidentate diazenido-ligand [Mo–N 1.770, 1.793(9)Å] and a chelating benzoyldiazene ligand [Mo–N 1.945, 1.945(8); Mo–O 2.130, 2.131(7)Å]. The chelate ring is planar in both molecules, indicating incorporation of the metal atom in the delocalised system.