Fluoride adducts of niobium(V): Activation reactions and alkene polymerizations

Fluoride coordination derivatives of niobium(V) were tested for their activation capabilities with respect to acetone and to olefins. Activation of acetone (formation of mesityloxide) was observed with NbF4 (OMe). Several fluoride coordination derivatives of niobium(V) of different nature (neutral or ionic) and nuclearity, i.e. NbF5L [L = Et2O, 4, thf, 5 (thf is tetrahydrofuran), MeOH, 6, EtOH, 7], (NbF4L2)(NbF6) [L = dmf, 8 (dmf is dimethylformamide), dme, 9 (dme is dimethoxyethane)], (NbF4L4)(NbF6) [L = thf, 10, Et2O, 11, MeCN, 12], [S(NMe)(3)][NbF6], 13, NbF4OMe, 1, NbF4OPh, 3), NbF3(OPh)(2), 14, NbF2(OPh)(3), 15 and NbF2(OEt)(3), 16, promoted the polymerization of ethylene using AlMe3-depleted methylaluminoxane as cocatalyst. Highly linear polyethylene was obtained. Compound 3, upon activation with methylaluminoxane, promoted ring-opening metathesis polymerization (ROMP) of norbornene, affording polymers with a slight excess of trans content.