Exploring the reactivity of tungsten bis(imido) dimethyl complexes with methyl aluminium reagents: implications for ethylene dimerization.

The reaction of [WCl2(NAr)2(DME)] (1) with excess Me3Al affords the dimethyl complex [WMe2(N{Ar}AlMe2{mu-Cl})(NAr)] (2), which on treatment with THF or MeAlCl2 yields [WMe2(NAr)2(THF)] (3) and [WMe2(N{Ar}AlMe(Cl){mu-Cl})(NAr)] (5), respectively. Complex 3 is unstable in solution dissociating to form [WMe2(NAr)2] (4) that may be isolated as an adduct with PMe3, [WMe2(NAr)2(PMe3)] (6). While complex 2 is inert towards ethylene, complex 3 reacts rapidly to afford a mixture of methane and but-1-ene (1:4). Neither complex 2 nor 3 react with propylene. Reaction of 3 with a C2H4/C2D4 (1:1) affords a mixture of isotopomers that is consistent with complete isotopic scrambling. The structures of complexes 1, 2, and 3 have been determined by X-ray diffraction.