The chemistry of molybdenum oxohydrazido(2—)-complexes; the X-ray crystal structure of [MoO(NNMe2)(C9H6NO)2], a complex with a bent hydrazido(2—)-ligand

Abstract

The oxohydrazido-complexes [MoO(NNR₂)(S₂CNR′₂)₂][R₂= Me₂, MePh, or (CH₂)₅; R′₂= Me₂, Et₂, or (CH₂)₅] react with an excess of acids HX (X = Cl, Br, SPh, ½ 1,2-O₂C₆H₄, or ½ 2,3-S₂C₆H₃CH₃) to give seven-co-ordinate [MoX₂(NNR₂)(S₂CNR′₂)₂]. For X = Cl or Br these complexes react with NaS₂CNR′₂ to give the cationic seven-co-ordinate [Mo(NNR₂)(S₂CNR′₂)₃]⁺. The complex [MoO(NNMe₂)(C₉H₆NO)₂] gives NHMe₂, NH₃, and Me₂NNH₂ on reaction with HCI and an X-ray crystal structure shows a significantly bent NNMe₂ ligand with MO–N–N 155.5°. The MO–N and N–N distances of 1.800(9) and 1.28(1)Å lie within the range found for other hydrazido(2–)-complexes. The complex ctystallises in the space group P2₁/a with a = 19.00(5), b= 14.59(4), c= 7.26(2)Å, and γ= 102.90(6)° for Z= 4. The final conventional error index, R, is equal to 0.087 for 2 747 reflections.