The chemistry of cyclopentadienyl nitrosyl and related complexes of molybdenum. Part 8. Carboxylato- and β-diketonato-complexes, their reactions with water, hydrogen sulphide, and alcohols, and the treatment of bis(cyclopentadienyl)iodonitrosylmolybdenum with some acids

Abstract

Reaction of [Mo(C₅H₅)₂I(NO)] with RCO₂H, or of [{Mo(η⁵-C₅H₅)(NO)X₂}₂] with Ag[O₂CR] affords [Mo-(η⁵-C₅H₅)(NO)(O₂CR)X](X = I, R = Me, Et, Prⁿ, Prⁱ, or Ph; X = Br, R = Me); the carboxylate group is bidentate. Treatment of [Mo(C₅H₅)₂I(NO)] with RCOCH₂OCR, or of [{Mo(η⁵-C₅H₅)I₂(NO)}₂] with TI[RCOCHOCR]affords [Mo(η⁵-C₅H₅)I(NO)(RCOCHOCR)](R = Me, CF₃, or Ph). Reaction of [Mo(η⁵-C₅H₅)(σ-C₅H₅)NO)(η²-S₂CNMe₂)] with CF₃CO₂H gives [Mo(η⁵-C₅H₅(NO)(σ-O₂CCF₃)(η²-S₂CNMe₂)], but a similar reaction does not occur with MeCO₂H. Both [Mo(η⁵-C₅H₅)I(NO)(O₂CMe)] and [Mo(η⁵-C₅H₅)I(NO)(MeCOCHOCMe)] react with MeOH or PhCH₂OH to give [{Mo(η⁵-C₅H₅)I(NO)(OR)}₂](R = Me or CH₂Ph), and methanolysis of [{Mo(η⁵-C₅H₅)(NO)(O₂CCF₃)₂}₂] affords [{Mo(η⁵-C₅H₅)(NO)(O₂CCF₃)(OMe)}₂]. With ‘wet’ alcohols (ROH: R = Et, Prⁿ, or Buⁿ) or water, [Mo(η⁵-C₅H₅)I(NO)(O₂CMe)] affords [(Mo(η⁵-C₅H₅)I(NO)(OH)}_n], and the corresponding deuteroxide is obtained via D₂O. Reaction of the acetatoiodide with H₂S gives [{Mo(η⁵-C₅H₅)(NO)(SH)}_n]. Treatment of [Mo(C₅H₅)₂I(NO)] with HPF₆ or HBF₄ in the presence of PPh₃ or Ph₂PCH₂CH₂PPh₂ gives [Mo(η⁵-C₅H₅)I(NO)(PPh₃)₂][PF₆] or [Mo(η⁵-C₅H₅)I(NO)(Ph₂PCH₂CH₂PPh₂)][BF₄], respectively. With HI or PhCH₂SH,[Mo(C₅H₅)₂I(NO)] affords [{Mo(η⁵-C₅H₅)I₂(NO)}₂] and [{Mo(η⁵-C₅H₅)I(NO)(SCH₂Ph)}₂], respectively.