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

The new compounds K[W(PMe3)H-3(5)], [K(18-crown-6)][W(PMe3)H-3(5)] (18-crown-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane), Na[W(PMe3)H-3(5)], [Na(15-crown-5)][W(PMe3)H-3(5)], (15-crown-5 = 1,4,7,10,13-pentaoxacyclopentadecane), [{W(PMe3)H-3(5)Li}4], K[W(eta-C5H5)(PMe3)H-4], [K(18-crown-6)][W(eta-C5H5)(PMe3)H-4], [K(18-crown-6)][W(eta-C5H4Et)(PMe3)H-4], K[cis-Re(PMe3)H-4(2)], [K(18-crown-6)][cis-Re(PMe3)H-4(2)], [W(PMe3(H-3(5)(SnBu(n)3)], [W(eta-C5H5)(PMe3)H-4(SnBu(n)3)], [Re(PMe3)H-4(2)(SnBu(n)3)], [H(eta-C5H5)2ZrW(PMe3)H-3(5)], [Cl(eta-C5H5)2ZrW(PMe3)H-3(5), [{(Ph3P)Au}3W(PMe3)H-3(4)]Cl.xCH2Cl2 and [K(18-crown-6)][Mo(eta-C5H5)H-2] are reported. The X-ray crystal structures of [K(18-crown-6)][W(PMe3)H-3(5)], [Na(15-crown-5)][W(PMe3)H-3(5)], [{W(PMe3)3H5Li}4], [K(18-crown-6)][cis-Re(PMe3)H-4(2)], [{(Ph3P)Au}3W(PMe3)H-3(4)]Cl.0.15CH2Cl2 and [K(18-crown-6)][Mo(eta-C5H5)H-2] have been determined. The crystal structures of [K(18-crown-6)][W(PMe3)H-3(5)] and [Na(15-crown-5)][W(PMe3)H-3(5)] 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.