Reactions of [M(NO){HB(3,5-Me2C3N2H)3}X2](M = Mo, X = I; M = W, X = Cl) with some amine-substituted pyridines. The molecular structures of [M(NO){HB(3,5-Me2C3N2H)3}(2-NHC5NH4)2]

Abstract

The 16-electron complex [Mo(NO){HB(3,5-Me₂C₃N₂H)₃}I₂] reacted with an excess of 2-amino-pyridine to produce the diamagnetic bis(amide) derivative [Mo(NO){HB(3,5-Me₂C₃N₂H)₃}(2-NHC₅NH₄)₂], whereas with 2-aminomethylpyridine the 17-electron complex [Mo(NO){HB(3,5-Me₂C₃N₂H)₃}(2-NH₂CH₂C₅NH₄)₂]⁺ was formed. Similar reactions with [W(NO){HB(3,5-Me₂C₃N₂H)₃}Cl₂] in the presence of NaH afforded only the bis(amide) derivatives. The molecular structures of [Mo(NO){HB(3,5-Me₂C₃N₂H)₃}(2-NHC₅NH₄)₂](M = Mo or W) were determined by X-ray diffraction methods. Both complexes contain metal ions in an approximately octahedral co-ordination environment with linear nitrosyl ligands. In neither case was evidence found for any interaction between the pyridyl nitrogen atom and the electron-deficient metal centre. The metal-nitrogen (amide) bond distances are 1.987(3) and 1.990(3)Å(Mo), and 1.97(1) and 2.00(1)Å(W). The corresponding M–NH–C(pyridyl) angles are 135.5(2), 135.4(2), 141(1), and 134(1)°, respectively.