Synthesis of [Mo(η-C5H4Pri)(PR3)2H3][R3= Me3 or Me2Ph), [Mo(η-C5H4Pri)(Pri2PCH2CH2PPri2)H3], and analogues and their ability to catalyse the photoinduced hydrogen–deuterium exchange of carbon–hydrogen bonds; crystal structure of [{Mo(η-C5H4Pri)(µ-Cl)2}2]

Abstract

Hydrochlorination of [Mo(η-C₅H₆)(σ,η-C₅H₄CMe₂)] gives [{Mo(η-C₅H₄Prⁱ)(µ-Cl)₂}₂] for which the crystal structure has been determined. This compound is a precursor to [Mo(η-C₅H₄Prⁱ)(PR₃)₂-Cl₂](R₃= Me₃ or Me₂Ph), [Mo(η-C₅H₄Prⁱ)(Prⁱ₂PCH₂CH₂PPrⁱ₂)₂Cl₂], [Mo(η-C₅H₄Prⁱ)(Me₂PCH₂CH₂-PMe₂)₂][ PF₆], [Mo(η-C₅H₄Prⁱ)(Me₂PCH₂CH₂PMe₂)₂H][PF₆], [Mo(η-C₅H₄Prⁱ)-trans-(PMe₃)₂Cl-cis-H₂], [Mo(η-C₅H₄Prⁱ)(PR₃)₂H₃], and [Mo(η-C₅H₄Prⁱ)(PMe₃)₂O][PF₆]. Photolysis of [Mo(ηC₅H₄)-(Me₂PCH₂CH₂PMe₂) H₃] in deuteriobenzene together with the substrates (CH₃)₂O, CH₃CO₂CH₃, toluene, mesitylene, ferrocene, bis(η-toluene)tungsten, and other organometallic compounds causes hydrogen–deuterium exchange between the C₆D₆ and some or all of the substrate hydrogens. The [ Mo(η-C₅H₄Prⁱ)(PR₃)₂H₃] derivatives are less active catalysts towards photoinduced H–D exchange reactions.