The chemistry of [W(PMe3)4(η2-CH2PMe2)H]: synthesis of hydroxy-hydrido, fluoro-hydrido, and silyl-hydrido derivatives and the dimerisation of ethylene and propene giving η4-diene derivatives. Crystal structure of [W(PMe3)4H2(OH2)F]F

Abstract

The syntheses of the compounds [W(PMe₃)₄H₂(OH)₂][BF₄]₂(2), [W(PMe₃)₄H₂(OH₂)F]F (3), [W(PMe₃)₄H₂F₂](4), [W(PMe₃)₄H₂(OH₂)F][PF₆](5), [W(PMe₃)₄H₂(O₂CCF₃)][CF₃CO₂](6)[W(PMe₃)₅H₂](7), [W(PMe₃)₄H₄](8), [W(PMe₃)₄H₂(SiH₃)₂](9), trans-[W(PMe₃)₄(η-C₂H₄)₂](12), cis-[W(PMe₃)₂(η-C₄H₆)₂](13), and [W(PMe₃)₃{η-CH₂C(Me)CHCH(syn-Me)}H₂](14) are described. They are formed by treatment of [W(PMe₃)₄(η²-CH₂PMe₂)H] with aqueous HBF₄, aqueous HF, aqueous HF then KH, aqueous HPF₆, CF₃COOH, H₂ in liquid PMe₃, H₂ in light petroleum, silane, ethylene, prolonged reaction with ethylene, or propene, respectively. Compounds (2)–(6), (9), and (14) are new. The crystal structure of (3) has been determined and contains a dodecahedral cation [W(PMe₃)₄H₂(OH₂)F]⁺ with which the counter anion F^– forms an ion pair via hydrogen bonding to the H₂O ligand.