Platinum‐Templated Coupling of B=N Units: Synthesis of BNBN Analogues of 1,3‐Dienes and a Butatriene

The 1:2 reaction of [μ‐(dmpm)Pt(nbe)](2) (dmpm=bis(dimethylphosphino)methane, nbe=norbornene) with Cl(2)BNR(SiMe(3)) (R=tBu, SiMe(3)) yields unsymmetrical (N‐aminoboryl)aminoboryl Pt(I) (2) complexes by B−N coupling via ClSiMe(3) elimination. A subsequent intramolecular ClSiMe(3) elimination from th...

Descripción completa

Detalles Bibliográficos
Autores principales: Brunecker, Carina, Arrowsmith, Merle, Fantuzzi, Felipe, Braunschweig, Holger
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8362192/
https://www.ncbi.nlm.nih.gov/pubmed/34036694
http://dx.doi.org/10.1002/anie.202106161
_version_ 1783738110653235200
author Brunecker, Carina
Arrowsmith, Merle
Fantuzzi, Felipe
Braunschweig, Holger
author_facet Brunecker, Carina
Arrowsmith, Merle
Fantuzzi, Felipe
Braunschweig, Holger
author_sort Brunecker, Carina
collection PubMed
description The 1:2 reaction of [μ‐(dmpm)Pt(nbe)](2) (dmpm=bis(dimethylphosphino)methane, nbe=norbornene) with Cl(2)BNR(SiMe(3)) (R=tBu, SiMe(3)) yields unsymmetrical (N‐aminoboryl)aminoboryl Pt(I) (2) complexes by B−N coupling via ClSiMe(3) elimination. A subsequent intramolecular ClSiMe(3) elimination from the tBu‐derivative leads to cyclization of the BNBN unit, forming a unique 1,3,2,4‐diazadiboretidin‐2‐yl ligand. In contrast, the analogous reaction with Br(2)BN(SiMe(3))(2) leads, via a twofold BrSiMe(3) elimination, to a Pt(II) (2) A‐frame complex bridged by a linear BNBN isostere of butatriene. Structural and computational data confirm π electron delocalization over the entire BNBN unit.
format Online
Article
Text
id pubmed-8362192
institution National Center for Biotechnology Information
language English
publishDate 2021
publisher John Wiley and Sons Inc.
record_format MEDLINE/PubMed
spelling pubmed-83621922021-08-17 Platinum‐Templated Coupling of B=N Units: Synthesis of BNBN Analogues of 1,3‐Dienes and a Butatriene Brunecker, Carina Arrowsmith, Merle Fantuzzi, Felipe Braunschweig, Holger Angew Chem Int Ed Engl Communications The 1:2 reaction of [μ‐(dmpm)Pt(nbe)](2) (dmpm=bis(dimethylphosphino)methane, nbe=norbornene) with Cl(2)BNR(SiMe(3)) (R=tBu, SiMe(3)) yields unsymmetrical (N‐aminoboryl)aminoboryl Pt(I) (2) complexes by B−N coupling via ClSiMe(3) elimination. A subsequent intramolecular ClSiMe(3) elimination from the tBu‐derivative leads to cyclization of the BNBN unit, forming a unique 1,3,2,4‐diazadiboretidin‐2‐yl ligand. In contrast, the analogous reaction with Br(2)BN(SiMe(3))(2) leads, via a twofold BrSiMe(3) elimination, to a Pt(II) (2) A‐frame complex bridged by a linear BNBN isostere of butatriene. Structural and computational data confirm π electron delocalization over the entire BNBN unit. John Wiley and Sons Inc. 2021-06-24 2021-07-26 /pmc/articles/PMC8362192/ /pubmed/34036694 http://dx.doi.org/10.1002/anie.202106161 Text en © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Communications
Brunecker, Carina
Arrowsmith, Merle
Fantuzzi, Felipe
Braunschweig, Holger
Platinum‐Templated Coupling of B=N Units: Synthesis of BNBN Analogues of 1,3‐Dienes and a Butatriene
title Platinum‐Templated Coupling of B=N Units: Synthesis of BNBN Analogues of 1,3‐Dienes and a Butatriene
title_full Platinum‐Templated Coupling of B=N Units: Synthesis of BNBN Analogues of 1,3‐Dienes and a Butatriene
title_fullStr Platinum‐Templated Coupling of B=N Units: Synthesis of BNBN Analogues of 1,3‐Dienes and a Butatriene
title_full_unstemmed Platinum‐Templated Coupling of B=N Units: Synthesis of BNBN Analogues of 1,3‐Dienes and a Butatriene
title_short Platinum‐Templated Coupling of B=N Units: Synthesis of BNBN Analogues of 1,3‐Dienes and a Butatriene
title_sort platinum‐templated coupling of b=n units: synthesis of bnbn analogues of 1,3‐dienes and a butatriene
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8362192/
https://www.ncbi.nlm.nih.gov/pubmed/34036694
http://dx.doi.org/10.1002/anie.202106161
work_keys_str_mv AT bruneckercarina platinumtemplatedcouplingofbnunitssynthesisofbnbnanaloguesof13dienesandabutatriene
AT arrowsmithmerle platinumtemplatedcouplingofbnunitssynthesisofbnbnanaloguesof13dienesandabutatriene
AT fantuzzifelipe platinumtemplatedcouplingofbnunitssynthesisofbnbnanaloguesof13dienesandabutatriene
AT braunschweigholger platinumtemplatedcouplingofbnunitssynthesisofbnbnanaloguesof13dienesandabutatriene

Ejemplares similares