Progress toward new catalysts for acyclic diene metathesis (ADMET) polymerization reactions

Article abstract of DOI:10.1016/0304-5102(92)80161-9

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°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 ('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.