Synthesis and isocyanate insertion reactions of tungsten(IV) imido complexes formed from W(CO)(acac)(N_3)(PMe_3)_3 with azide as the oxidant

摘要

Addition of excess trimethylphosphine and a halide source to a solution of W(CO)(acac)_2(η~2-L) (L = NCPh and OCMe_2) leads to displacement of L and one acetylacetonate chelate to produce electron-rich, seven-coordinate complexes of the formula W(CO)(acac)(X)(PMe _3)_3 (X = Cl, Br, and I). Use of NaN3 instead of a halide source leads primarily to loss of carbon monoxide and dinitrogen, and protonation from adventitious water yields the cationic imido complex [W(NH)(acac)(PMe_3)_3]~+. Heating [W(NH)(acac)(PMe_3)_3]~+ in aromatic isocyanates at high temperature results in isocyanate insertion into the NH imido bond to form new C-N bonds. An alternate route to related imido complexes involves heating [W(O)(acac)(PMe_3)_3]~+ with phenyl isocyanate at high temperatures to yield the substituted imido complex [W(NPh)(acac)(PMe_3)_3]~+.