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Issue 21, 2019
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Stereospecific polymerization of conjugated dienes using neodymium alkylborohydride complexes

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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.

Graphical abstract: Stereospecific polymerization of conjugated dienes using neodymium alkylborohydride complexes

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Publication details

The article was received on 23 Oct 2018, accepted on 08 Feb 2019 and first published on 08 Feb 2019


Article type: Paper
DOI: 10.1039/C8DT04220A
Dalton Trans., 2019,48, 7267-7273

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    Stereospecific polymerization of conjugated dienes using neodymium alkylborohydride complexes

    R. Tanaka, Y. Shinto, R. Matsuzaki, Y. Nakayama and T. Shiono, Dalton Trans., 2019, 48, 7267
    DOI: 10.1039/C8DT04220A

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