The chemistry of cyclopentadienyl nitrosyl complexes of molybdenum. Part 11. Monohapto-allylic species and their reactions with electrophiles

Abstract

Treatment of [Mo(η⁵-C₅H₅)(η³-C₃H₅)l(NO)] or [Mo(η⁵-C₅H₅)(η³-C₃H₅)(NO)(NCMe)][PF₆] with NaS₂CNR₂ or AgOCOC₂F₅ affords [Mo(η⁵-C₅H₅)(η¹-C₃H₅)(NO)(S₂CNR₂)], (1; R = Me or Et) and [Mo(η⁵-C₅H₅)(η³-C₃H₅)(NO){OC(:O)C₂F₅}], respectively. The structures of these compounds are discussed. Treatment of (1) with electrophiles (EX) gives either cyclisation products, [Mo(η⁵-C₅H₅)([graphic omitted]H₂)(NO)(S₂CNR₂)], [EX = C₂(CN)₄ or (CF₃)₂CO] or insertion products [Mo(η⁵-C₅H₅)(EXCH₂CH:CH₂)(NO)(S₂CNMe₂)](EX = CF₃C₂CF₃ or SO₂). Treatment of (1; R = Me) with HCl and SOCl₂ affords [Mo(η⁵-C₅H₅)Cl(NO)(S₂CNMe₂)] and [Mo(η⁵-C₅H₅)(C₃H₅SOCl₂)(NO)(S₂CNMe₂)], respectively. The properties of (1) are compared with those of [Mo(η⁵-C₅H₅)(η¹-C₅H₅)(NO)(S₂CNMe₂)] and [Mo(C₅H₅)₂I(NO)].