Step-growth titanium-catalysed dehydropolymerisation of amine-boranes

Chemical Science
Titel JurcaIan Manners

Abstract

Precatalysts active for the dehydropolymerisation of primary amine-boranes are generally based on mid or late transition metal. We have found that the activity of the precatalyst system formed from CpR2TiCl2 and 2nBuLi towards the dehydrogenation of the secondary amine-borane Me2NH·BH3, to yield the cyclic diborazane [Me2N-BH2]2, increases dramatically with increasing electron-donating character of the cyclopentadienyl rings (CpR). Application of the most active precatalyst system (CpR = η-C5Me5) to the primary amine-borane MeNH2·BH3 enabled the first synthesis of high molar mass poly(N-methylaminoborane), [MeNH-BH2] n , the BN analogue of polypropylene, by an early transition metal such as catalyst. Significantly, unlike other dehydropolymerization precatalysts for MeNH2·BH3 such as [Ir(POCOP)H2], skeletal nickel, and [Rh(COD)Cl]2, the Ti precatalyst system was also active towards a range of substrates including BzNH2·BH3 (Bz = benzyl) yielding high molar mass polymer. Moreover, in contrast to the late transition metal catalysed dehydropolymerisation of MeNH2·BH3 and also the Ziegler-Natta polymerisation of olefins, studies indicate that the Ti-catalyzed dehydropolymerization reactions proceed by a step-growth rather than a ...Continue Reading

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Citations

Aug 30, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·M TroseT Beweries
Nov 1, 2018·Chemistry : a European Journal·Thomas M MaierRobert Wolf
Oct 20, 2018·Chemistry : a European Journal·Annie L Colebatch, Andrew S Weller
Nov 15, 2018·Angewandte Chemie·Fernando Vidal, Frieder Jäkle
Mar 14, 2019·Chemistry : a European Journal·Estefanía Del HornoCarlos Yélamos
Apr 17, 2019·Nature Reviews. Chemistry·Evan P BeaumierIan A Tonks
Dec 13, 2019·Chemical Communications : Chem Comm·Timothy M BoydAndrew S Weller
Dec 1, 2021·Journal of the American Chemical Society·Claire N BrodieAndrew S Weller

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Methods Mentioned

BETA
NMR

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