PROGRESS TOWARD NEW CATALYSTS FOR ACYCLIC DIENE METATHESIS (ADMET) POLYMERIZATION REACTIONS

The compounds Tp'W(CHR)(E)X (Tp' = hydridotris(3,5-dimethylpyrazolyl)borate; R = CMe3, Ph; E = O, NPh; X = Cl, Br), 4a-c, have been synthesized by reaction of Tp'W(CR)X2 (R = CMe3, X = Cl; R = Ph, X = Br), 3a,b, with neutral alumina or aniline. Compounds 3a,b and 4a - c are air stable and thermally stable to > 100-degrees-C in the solid state. When combined with 1 equivalent of AlCl3, Tp'W(CHPh)(NPh)Br, 4c, catalyzes the acyclic diene metathesis (ADMET) oligomerization of 1,9-decadiene, giving a mixture of 1,9,17-octadecatriene, 1,9,17,25-hexadodecatetraene and ethylene (almost-equal-to 30% conversion). The new alkylidene complex, 4a, is an efficient ring-opening metathesis polymerization (ROMP) catalyst in the presence of AlCl3 as a co-catalyst.