ABSTRACT
Two neodymium alkylborohydride complexes that differ with respect to the number of hydrides on the boron center were synthesized and characterized. The µ2-ligated complex exhibits Nd-B bond lengths that are approximately 10% longer than those in previously reported µ3-ligated borohydride complexes. For the µ3-alkylborohydride complex, the Nd-H-B stretching bands observed by IR spectroscopy suggested stronger borohydride coordination than that of [BH4]-, which is probably due to the electron donation of the alkyl groups. These newly prepared complexes successfully promoted trans-1,4 specific polymerization of conjugate dienes upon activation by Bu2Mg, whereas activation of these complexes by Bu2Mg/MMAO gave cis-1,4 regular polymer. The trans-1,4 defect of the polyisoprene obtained from the Nd µ2-alkylborohydride complex/Bu2Mg/MMAO system (<2%) was much lower than that obtained from previously reported µ3-BH4-ligated neodymium complex (11%). Moreover, µ2-alkylborohydride complex was a good initiator for the polymerization of MMA, probably because of its anionic nature.
