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Synthesis of Unsymmetrical Diboron(5) Compounds and Their Conversion to Diboron(5) Cations

Please always quote using this URN: urn:nbn:de:bvb:20-opus-164299
  • Reaction of bis-catecholatodiboron-NHC adducts, B\(_2\)Cat\(_2\)(NHC), (NHC = IMe (tetramethylimidazol-2-ylidene), IMes (1,3-dimesitylimidazol-2-ylidene) or IDIPP (1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)) with BCl3 results in the replacement of the catecholato group bound to the four coordinate boron with two chlorides to yield diboron(5) Lewis acid-base adducts of formula CatB-BCl\(_2\)(NHC). These compounds are precursors to diboron(5) monocations, accessed by adding AlCl\(_3\) or K[B(C\(_6\)F\(_5\))\(_4\)] as halide abstractionReaction of bis-catecholatodiboron-NHC adducts, B\(_2\)Cat\(_2\)(NHC), (NHC = IMe (tetramethylimidazol-2-ylidene), IMes (1,3-dimesitylimidazol-2-ylidene) or IDIPP (1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)) with BCl3 results in the replacement of the catecholato group bound to the four coordinate boron with two chlorides to yield diboron(5) Lewis acid-base adducts of formula CatB-BCl\(_2\)(NHC). These compounds are precursors to diboron(5) monocations, accessed by adding AlCl\(_3\) or K[B(C\(_6\)F\(_5\))\(_4\)] as halide abstraction agents in the presence of a Lewis base. The substitution of the chlorides of CatB-BCl\(_2\)(NHC) for hydrides is achieved using Bu\(_3\)SnH and a halide abstracting agent to form 1,1-dihydrodiboron(5) compounds, CatB-BH\(_2\)(NHC). Attempts to generate diboron(4) monocations of formula [CatB-B(Y)(NHC)]\(^+\) (Y = Cl or H) led to the rapid formation of CatBY.show moreshow less

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Metadaten
Author: Jessica Cid, Alexander Hermann, James E. Radcliffe, Liam D. Curless, Holger BraunschweigORCiD, Michael J. Ingleson
URN:urn:nbn:de:bvb:20-opus-164299
Document Type:Preprint
Faculties:Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie
Language:English
Parent Title (English):Organometallics
Year of Completion:2018
Source:Organometallics, 2018, 37 (12), pp 1992–1998 DOI: 10.1021/acs.organomet.8b00288
DOI:https://doi.org/10.1021/acs.organomet.8b00288
Dewey Decimal Classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 546 Anorganische Chemie
Tag:Lewis acids; boron; boronium cations; diboron; electrophiles
Release Date:2018/07/24
Note:
This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in Organometallics, copyright © 2018 American Chemical Society after peer review. To access the final edited and published work see dx.doi.org/10.1021/acs.organomet.8b00288
EU-Project number / Contract (GA) number:669054
OpenAIRE:OpenAIRE
Licence (German):License LogoDeutsches Urheberrecht