Transition metal–hydrogen–alkali metal bonds: synthesis and crystal structures of [K(18-crown-6)][W(PMe3)3H5], [Na(15-crown-5)][W(PMe3)3H5] and [{W(PMe3)3H5Li}4] and related studies

Abstract

The new compounds K[W(PMe₃)₃H₅], [K(18-crown-6)][W(PMe₃)₃H₅](18-crown-6 = 1,4,7,10,13,16-hexaoxacycloctadecane), Na[W(PMe₃)₃H₅], [Na(15-crown-5)][W(PMe₃)₃H₅], (15-crown-5 = 1,4,7,10,13-pentaoxacyclopentadecane), [{W(PMe₃)₃H₅Li}₄], K[W(η-C₅H₅)(PMe₃)H₄], [K(18-crown-6)][W(η-C₅H₅)(PMe₃)H₄], [K(18-crown-6)][W(η-C₅H₄Et)(PMe₃)H₄], K[cis-Re(PMe₃)₄H₂], [K(18-crown-6)][cis-Re(PMe₃)₄H₂], [W(PMe₃)₃H₅(SnBuⁿ₃)], [W(ηC₅H₅)(PMe₃)H₄(SnBuⁿ₃)], [Re(PMe₃)₄H₂(SnBuⁿ₃)], [H(η-C₅H₅)₂ZrW(PMe₃)₃H₅], [Cl(η-C₅H₅)₂ZrW(PMe₃)₃H₅], [{(Ph₃P)Au}₃W(PMe₃)₃H₄]Cl·xCH₂Cl₂ and [K(18-crown-6)][Mo(η-C₅H₅)₂H] are reported. The X-ray crystal structures of [K(18-crown-6)][W(PMe₃)₃H₅], [Na(15-crown-5)][W(PMe₃)₃H₅], [{W(PMe₃)₃H₅Li}₄], [K(18-crown-6)][cis-Re(PMe₃)₄H₂], [{(Ph₃P)Au}₃W(PMe₃)₃H₄]Cl·0.15CH₂Cl₂ and [K(18-crown-6)][Mo(η-C₅H₅)₂H] have been determined. The crystal structures of [K(18-crown-6)][W(PMe₃)₃H₅] and [Na(15-crown-5)][W(PMe₃)₃H₅] have also been determined by neutron diffraction. Evidence for the presence of a degree of covalent bonding in the systems M–H–M′, where M = W and M′= Li, Na or K and M = Re, M′= K, is discussed.