RT Journal Article
T1 Dehydropolymerization of Amine-Boranes using Bis(imino)pyridine Rhodium Pre-Catalysis: σ-Amine-Borane Complexes, Nanoparticles, and Low Residual-Metal BN-Polymers that can be Chemically Repurposed
A1 Cross, Mathew J.
A1 Brodie, Claire N.
A1 Crivoi, Dana G.
A1 Goodall, Joe C.
A1 Ryan, David E.
A1 Martínez Martínez, Antonio Jesús
A1 Johnson, Alice
A1 Weller, Andrew S.
AB The sigma amine-borane complexes [Rh(L1)(η2:η2-H3B·NRH2)][OTf] (L1=2,6-bis-[1-(2,6-diisopropylphenylimino) ethyl]pyridine, R=Me, Et, nPr) are described, alongside [Rh-(L1)(NMeH2)][OTf]. Using R=Me as a pre-catalyst (1 mol%) the dehydropolymerization of H3B·NMeH2 gives [H2BNMeH]n selectively. Added NMeH2, or the direct use of [Rh(L1)(NMeH2)][OTf], is required for initiation of catalysis, which is suggested to operate through the formation of a neutral hydride complex,Rh(L1)H. The formation of small (1–5 nm) nanoparticles isobserved at the end of catalysis, but studies are ambiguous asto whether the catalysis is solely nanoparticle promoted or ifthere is a molecular homogeneous component. [Rh-(L1)(NMeH2)][OTf] is shown to operate at 0.025 mol% loadingson a 2 g scale of H3B·NMeH2 to give polyaminoborane[H2BNMeH]n [Mn=30,900 g/mol, Ð=1.8] that can be purified toa low residual [Rh] (6 μg/g). Addition of Na[N(SiMe3)2] to[H2BNMeH]n results in selective depolymerization to form theeee-isomer of N,N,N-trimethylcyclotriborazane [H2BNMeH]3: thechemical repurposing of a main-group polymer.
PB Wiley
SN 0947-6539
SN 1521-3765 (electrónico)
YR 2023
FD 2023
LK https://hdl.handle.net/10272/23275
UL https://hdl.handle.net/10272/23275
LA eng
NO Cross, M. J., Brodie, C. N., Crivoi, D. G., Goodall, J. C., Ryan, D. E., Martínez‐Martínez, A. J., Johnson, A., & Weller, A. S. (2023). Dehydropolymerization of Amine−Boranes using Bis(imino)pyridine Rhodium Pre‐Catalysis: σ‐Amine−Borane Complexes, Nanoparticles, and Low Residual‐Metal BN−Polymers that can be Chemically Repurposed. In Chemistry – A European Journal (Vol. 29, Issue 60). Wiley. https://doi.org/10.1002/chem.202302110
NO EPSRC EP/M024210, SCG Chemicals Co. Ltd, University of York.We are grateful for computational support from the Universityof York High Performance Computing service, Viking and theResearch Computing team.
DS Repositorio Institucional de la Universidad de Huelva
RD 30 may 2026