Tuning the catalytic properties of rare earth borohydrides for the polymerisation of isoprene

Abstract

Previous results obtained for the cis-polymerisation of isoprene with scandium half-sandwich complex Cp*Sc(BH(4))(2)(THF) 1a were extended to its neodymium analog. The X-ray structure of the already reported neodymium monomer compound Cp*Nd(BH(4))(2)(THF)(2) 1b is presented. Cp*Nd(BH(4))(2)(THF)(2)/[CPh(3)][B(C(6)F(5))(4)]/Al((i)Bu)(3) catalytic system was found to be very active and stereoselective towards isoprene polymerisation, leading to highly 1,4-cis polyisoprene up to 92%. The effect on isoprene polymerisation of the addition of a NHC molecule to Cp*Ln(BH(4))(2)(THF)(n) pre-catalyst (Cp* = η(5)-C(5)Me(5), Ln = Sc, n = 1, 1a; Nd, n = 2, 1b; Sm, n = 2, 1c) or to a trisborohydride Ln(BH(4))(3)(THF)(n) (Ln = Sc, n = 1.5, 2a; Nd, n = 3, 2b; Sm, n = 3, 2c) was also studied. Several NHC ligands were assessed: the classical [1-C{(N(t)BuCH)}(2)] (L(1)) and functional N-heterocyclic carbenes, two amino-tethered HNBu(t)CH(2)CH(2)[1-C{N(CHCH)NR}] (HL(2-R)) (R = (t)Bu, Mes (Mes = 2,4,6-Me(3)-C(6)H(2))) and the hydroxyl-tethered HOCMe(2)CH(2)[1-C{N(CHCH)N(i)Pr}] (HL(3)). Neodymium-based complex (L(2-tBu))Nd(BH(4))(2)(THF)(2) 3 could be isolated and characterized. With some of the catalytic combinations tested, the introduction of the NHC ligand in the coordination sphere of the complex induces a switch of the stereoselectivity of the resulting polymer. Scandium complex 2a, which produces mainly 1,4-cis polyisoprene when associated to a borate activator and aluminum alkyl, leads to 1,4-trans polymer up to 94% regular when HL(2-tBu) carbene is added to the same reaction mixture. This result is the only example of highly trans-polyisoprene synthesized with a scandium based catalyst. Coordination of the carbene moiety to the rare earth centre is confirmed by NMR studies on paramagnetic neodymium pre-catalysts.