Hydrogen-bonded tetramethylethylenediammonium and triphenylphosphonium complexes derived from liquid clathrate media

Reactions of M(CO)(6) with HCl(g) in the presence of tetramethylethylenedia mine (=tmeda) and H2O (M=W) or in the presence of triphenylphosphine and H2 O (M=Mo) have been investigated. These reactions were performed in aromatic media and were promoted by UV radiation; solutions immediately separated i nto two layers indicative of liquid clathrate formation. In both, a M-V spe cies was obtained, the former being [(H+)(2)tmeda][H+. HNMe2][WOCl4(H2O)(-) ]-[Cl-](2), 1, while for the latter [H+. PPh3](2)[MoOCl52-], 2 resulted. X- ray crystal structures were performed on each compound. The structure of 1 showed two distinct structural features, {[(H+)(2)tmeda] [Cl-]}(2)(2+) dime rs with Cl- ions hydrogen-bonded through N-H ... Cl ... H-N bridges and {[H +. HNMe2][WOCl4(H2O)(-)][Cl-]}(2)(2-) dimers where Cl- ions bridge through O(H2O)-H ... Cl ... H-N hydrogen bonds. Another interesting feature of this compound is the cleavage of the tmeda ligand to form the H+. HNMe2 cation. In complex 2 both of the triphenylphosphine ligands are protonated and are bound to the [MoOCl52-]anion through P-H ... Cl hydrogen bonds.