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Synthesis and hydrogenation of polycyclic aromatic hydrocarbon-substituted diborenes via uncatalysed hydrogenative B–C bond cleavage
The classical route to the PMe(3)-stabilised polycyclic aromatic hydrocarbon (PAH)-substituted diborenes B(2)Ar(2)(PMe(3))(2) (Ar = 9-phenanthryl 7-Phen; Ar = 1-pyrenyl 7-Pyr) via the corresponding 1,2-diaryl-1,2-dimethoxydiborane(4) precursors, B(2)Ar(2)(OMe)(2), is marred by the systematic decompo...
Autores principales: | , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9242019/ https://www.ncbi.nlm.nih.gov/pubmed/35872817 http://dx.doi.org/10.1039/d2sc02515a |
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author | Okorn, Alexander Jayaraman, Arumugam Englert, Lukas Arrowsmith, Merle Swoboda, Theresa Weigelt, Jeanette Brunecker, Carina Hess, Merlin Lamprecht, Anna Lenczyk, Carsten Rang, Maximilian Braunschweig, Holger |
author_facet | Okorn, Alexander Jayaraman, Arumugam Englert, Lukas Arrowsmith, Merle Swoboda, Theresa Weigelt, Jeanette Brunecker, Carina Hess, Merlin Lamprecht, Anna Lenczyk, Carsten Rang, Maximilian Braunschweig, Holger |
author_sort | Okorn, Alexander |
collection | PubMed |
description | The classical route to the PMe(3)-stabilised polycyclic aromatic hydrocarbon (PAH)-substituted diborenes B(2)Ar(2)(PMe(3))(2) (Ar = 9-phenanthryl 7-Phen; Ar = 1-pyrenyl 7-Pyr) via the corresponding 1,2-diaryl-1,2-dimethoxydiborane(4) precursors, B(2)Ar(2)(OMe)(2), is marred by the systematic decomposition of the latter to BAr(OMe)(2) during reaction workup. Calculations suggest this results from the absence of a second ortho-substituent on the boron-bound aryl rings, which enables their free rotation and exposes the B–B bond to nucleophilic attack. 7-Phen and 7-Pyr are obtained by the reduction of the corresponding 1,2-diaryl-1,2-dichlorodiborane precursors, B(2)Ar(2)Cl(2)(PMe(3))(2), obtained from the SMe(2) adducts, which are synthesised by direct NMe(2)–Cl exchange at B(2)Ar(2)(NMe(2))(2) with (Me(2)S)BCl(3). The low-lying π* molecular orbitals (MOs) located on the PAH substituents of 7-Phen and 7-Pyr intercalate between the B–B-based π and π* MOs, leading to a relatively small HOMO–LUMO gap of 3.20 and 2.72 eV, respectively. Under vacuum or at high temperature 7-Phen and 7-Pyr undergo intramolecular hydroarylation of the B[double bond, length as m-dash]B bond to yield 1,2-dihydronaphtho[1,8-cd][1,2]diborole derivatives. Hydrogenation of 7-Phen, 7-Pyr and their 9-anthryl and mesityl analogues III and II, respectively, results in all cases in splitting of the B–B bond and isolation of the monoboranes (Me(3)P)BArH(2). NMR-spectroscopic monitoring of the reactions, solid-state structures of isolated reaction intermediates and computational mechanistic analyses show that the hydrogenation of the three PAH-substituted diborenes proceeds via a different pathway to that of the dimesityldiborene. Rather than occurring exclusively at the B–B bond, hydrogenation of 7-Ar and III proceeds via a hydroarylated intermediate, which undergoes one B–B bond-centered H(2) addition, followed by hydrogenation of the endocyclic B–C bond resulting from hydroarylation, making the latter effectively reversible. |
format | Online Article Text |
id | pubmed-9242019 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-92420192022-07-22 Synthesis and hydrogenation of polycyclic aromatic hydrocarbon-substituted diborenes via uncatalysed hydrogenative B–C bond cleavage Okorn, Alexander Jayaraman, Arumugam Englert, Lukas Arrowsmith, Merle Swoboda, Theresa Weigelt, Jeanette Brunecker, Carina Hess, Merlin Lamprecht, Anna Lenczyk, Carsten Rang, Maximilian Braunschweig, Holger Chem Sci Chemistry The classical route to the PMe(3)-stabilised polycyclic aromatic hydrocarbon (PAH)-substituted diborenes B(2)Ar(2)(PMe(3))(2) (Ar = 9-phenanthryl 7-Phen; Ar = 1-pyrenyl 7-Pyr) via the corresponding 1,2-diaryl-1,2-dimethoxydiborane(4) precursors, B(2)Ar(2)(OMe)(2), is marred by the systematic decomposition of the latter to BAr(OMe)(2) during reaction workup. Calculations suggest this results from the absence of a second ortho-substituent on the boron-bound aryl rings, which enables their free rotation and exposes the B–B bond to nucleophilic attack. 7-Phen and 7-Pyr are obtained by the reduction of the corresponding 1,2-diaryl-1,2-dichlorodiborane precursors, B(2)Ar(2)Cl(2)(PMe(3))(2), obtained from the SMe(2) adducts, which are synthesised by direct NMe(2)–Cl exchange at B(2)Ar(2)(NMe(2))(2) with (Me(2)S)BCl(3). The low-lying π* molecular orbitals (MOs) located on the PAH substituents of 7-Phen and 7-Pyr intercalate between the B–B-based π and π* MOs, leading to a relatively small HOMO–LUMO gap of 3.20 and 2.72 eV, respectively. Under vacuum or at high temperature 7-Phen and 7-Pyr undergo intramolecular hydroarylation of the B[double bond, length as m-dash]B bond to yield 1,2-dihydronaphtho[1,8-cd][1,2]diborole derivatives. Hydrogenation of 7-Phen, 7-Pyr and their 9-anthryl and mesityl analogues III and II, respectively, results in all cases in splitting of the B–B bond and isolation of the monoboranes (Me(3)P)BArH(2). NMR-spectroscopic monitoring of the reactions, solid-state structures of isolated reaction intermediates and computational mechanistic analyses show that the hydrogenation of the three PAH-substituted diborenes proceeds via a different pathway to that of the dimesityldiborene. Rather than occurring exclusively at the B–B bond, hydrogenation of 7-Ar and III proceeds via a hydroarylated intermediate, which undergoes one B–B bond-centered H(2) addition, followed by hydrogenation of the endocyclic B–C bond resulting from hydroarylation, making the latter effectively reversible. The Royal Society of Chemistry 2022-06-14 /pmc/articles/PMC9242019/ /pubmed/35872817 http://dx.doi.org/10.1039/d2sc02515a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Okorn, Alexander Jayaraman, Arumugam Englert, Lukas Arrowsmith, Merle Swoboda, Theresa Weigelt, Jeanette Brunecker, Carina Hess, Merlin Lamprecht, Anna Lenczyk, Carsten Rang, Maximilian Braunschweig, Holger Synthesis and hydrogenation of polycyclic aromatic hydrocarbon-substituted diborenes via uncatalysed hydrogenative B–C bond cleavage |
title | Synthesis and hydrogenation of polycyclic aromatic hydrocarbon-substituted diborenes via uncatalysed hydrogenative B–C bond cleavage |
title_full | Synthesis and hydrogenation of polycyclic aromatic hydrocarbon-substituted diborenes via uncatalysed hydrogenative B–C bond cleavage |
title_fullStr | Synthesis and hydrogenation of polycyclic aromatic hydrocarbon-substituted diborenes via uncatalysed hydrogenative B–C bond cleavage |
title_full_unstemmed | Synthesis and hydrogenation of polycyclic aromatic hydrocarbon-substituted diborenes via uncatalysed hydrogenative B–C bond cleavage |
title_short | Synthesis and hydrogenation of polycyclic aromatic hydrocarbon-substituted diborenes via uncatalysed hydrogenative B–C bond cleavage |
title_sort | synthesis and hydrogenation of polycyclic aromatic hydrocarbon-substituted diborenes via uncatalysed hydrogenative b–c bond cleavage |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9242019/ https://www.ncbi.nlm.nih.gov/pubmed/35872817 http://dx.doi.org/10.1039/d2sc02515a |
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