Reactivity of acetone oxime towards oxomolybdenum(VI) complexes. Part 2. Syntheses, crystal structures and reactivity of molybdenum nitrosyl complexes

Abstract

The complexes [Mo(NO)(acac)₂(Me₂CNO)]1(acac = acetylacetonate), [{Mo(NO)(OR)(Me₂CNO)₂}₂](R = Me 2a or Et 2b) and [Mo₂(NO)₂(OR)₂Cl(Me₂CNO)₃(Me₂CNHO)](R = Me 3a or Et 3b) have been obtained by reductive nitrosylation of [MoO₂(acac)₂], [NBuⁿ₄]₂[Mo₆O₁₉] and [NBuⁿ₄]₂[Mo₄O₁₂(Me₂CNO)₂], respectively, by acetone oxime in methanol or ethanol under reflux. Complex 2a reacts with [NBuⁿ₄]₂[Mo₂O₇] to yield [NBuⁿ₄]₂[Mo₄O₁₀(NO)(OMe)(Me₂CNO)₂]4. This suggests that the reaction of molybdenum(II) nitrosyl complexes with polyoxomolybdates could be a route to a variety of oxonitrosyl species. Crystal structure determinations for 1, 2b, 3b and 4 give further insight into the rich co-ordination chemistry of acetone oxime and reveal an unprecedented µ₃-κN:κ²O co-ordination mode.