{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Cross MJ"],"funding":["SCG Chemicals","Engineering and Physical Sciences Research Council"],"pagination":["e202302110"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC10947130"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["29(60)"],"pubmed_abstract":["The sigma amine-borane complexes [Rh(L1)(η<sup>2</sup> :η<sup>2</sup> -H<sub>3</sub> B⋅NRH<sub>2</sub> )][OTf] (L1=2,6-bis-[1-(2,6-diisopropylphenylimino)ethyl]pyridine, R=Me, Et, <sup>n</sup> Pr) are described, alongside [Rh(L1)(NMeH<sub>2</sub> )][OTf]. Using R=Me as a pre-catalyst (1 mol %) the dehydropolymerization of H<sub>3</sub> B ⋅ NMeH<sub>2</sub> gives [H<sub>2</sub> BNMeH]<sub>n</sub> selectively. Added NMeH<sub>2</sub> , or the direct use of [Rh(L1)(NMeH<sub>2</sub> )][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 is observed at the end of catalysis, but studies are ambiguous as to whether the catalysis is solely nanoparticle promoted or if there is a molecular homogeneous component. [Rh(L1)(NMeH<sub>2</sub> )][OTf] is shown to operate at 0.025 mol % loadings on a 2 g scale of H<sub>3</sub> B ⋅ NMeH<sub>2</sub> to give polyaminoborane [H<sub>2</sub> BNMeH]<sub>n</sub> [M<sub>n</sub> =30,900 g/mol, Ð=1.8] that can be purified to a low residual [Rh] (6 μg/g). Addition of Na[N(SiMe<sub>3</sub> )<sub>2</sub> ] to [H<sub>2</sub> BNMeH]<sub>n</sub> results in selective depolymerization to form the eee-isomer of N,N,N-trimethylcyclotriborazane [H<sub>2</sub> BNMeH]<sub>3</sub> : the chemical repurposing of a main-group polymer."],"journal":["Chemistry (Weinheim an der Bergstrasse, Germany)"],"pubmed_title":["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."],"pmcid":["PMC10947130"],"funding_grant_id":["EP/M024210"],"pubmed_authors":["Goodall JC","Martinez-Martinez AJ","Brodie CN","Cross MJ","Crivoi DG","Johnson A","Ryan DE","Weller AS"],"additional_accession":[]},"is_claimable":false,"name":"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.","description":"The sigma amine-borane complexes [Rh(L1)(η<sup>2</sup> :η<sup>2</sup> -H<sub>3</sub> B⋅NRH<sub>2</sub> )][OTf] (L1=2,6-bis-[1-(2,6-diisopropylphenylimino)ethyl]pyridine, R=Me, Et, <sup>n</sup> Pr) are described, alongside [Rh(L1)(NMeH<sub>2</sub> )][OTf]. Using R=Me as a pre-catalyst (1 mol %) the dehydropolymerization of H<sub>3</sub> B ⋅ NMeH<sub>2</sub> gives [H<sub>2</sub> BNMeH]<sub>n</sub> selectively. Added NMeH<sub>2</sub> , or the direct use of [Rh(L1)(NMeH<sub>2</sub> )][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 is observed at the end of catalysis, but studies are ambiguous as to whether the catalysis is solely nanoparticle promoted or if there is a molecular homogeneous component. [Rh(L1)(NMeH<sub>2</sub> )][OTf] is shown to operate at 0.025 mol % loadings on a 2 g scale of H<sub>3</sub> B ⋅ NMeH<sub>2</sub> to give polyaminoborane [H<sub>2</sub> BNMeH]<sub>n</sub> [M<sub>n</sub> =30,900 g/mol, Ð=1.8] that can be purified to a low residual [Rh] (6 μg/g). Addition of Na[N(SiMe<sub>3</sub> )<sub>2</sub> ] to [H<sub>2</sub> BNMeH]<sub>n</sub> results in selective depolymerization to form the eee-isomer of N,N,N-trimethylcyclotriborazane [H<sub>2</sub> BNMeH]<sub>3</sub> : the chemical repurposing of a main-group polymer.","dates":{"release":"2023-01-01T00:00:00Z","publication":"2023 Oct","modification":"2025-04-20T02:47:45.887Z","creation":"2025-02-19T03:08:18.516Z"},"accession":"S-EPMC10947130","cross_references":{"pubmed":["37530441"],"doi":["10.1002/chem.202302110"]}}