Platinum‐Templated Coupling of B=N Units: Synthesis of BNBN Analogues of 1,3‐Dienes and a Butatriene
| Autor: | Felipe Fantuzzi, Holger Braunschweig, Merle Arrowsmith, Carina Brunecker |
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| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
1
3 2 4-diazadiboretidin-2-yl ligand 010405 organic chemistry Isostere Chemistry Ligand A-frame complex Communication Electron delocalization isosterism chemistry.chemical_element General Chemistry 010402 general chemistry 01 natural sciences Medicinal chemistry Catalysis Communications B−N Coupling 0104 chemical sciences Coupling (electronics) chemistry.chemical_compound Intramolecular force butatriene analogue QD Platinum Norbornene |
| Zdroj: | Angewandte Chemie (International Ed. in English) |
| ISSN: | 1521-3773 1433-7851 |
| Popis: | The 1:2 reaction of [μ‐(dmpm)Pt(nbe)]2 (dmpm=bis(dimethylphosphino)methane, nbe=norbornene) with Cl2BNR(SiMe3) (R=tBu, SiMe3) yields unsymmetrical (N‐aminoboryl)aminoboryl PtI 2 complexes by B−N coupling via ClSiMe3 elimination. A subsequent intramolecular ClSiMe3 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 Br2BN(SiMe3)2 leads, via a twofold BrSiMe3 elimination, to a PtII 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. The [μ‐(dmpm)Pt]2 template promotes the coupling of B=N units derived from dihalo(silylamino)borane precursors by B−N bond formation through intermolecular halosilane elimination. For Cl2BNR(SiMe3) η1‐(N‐aminoboryl)aminoboryl and η1‐1,3,2,4‐diazaboretidin‐2‐yl PtI 2 complexes are obtained, whereas for Br2BN(SiMe3)2 an A‐frame complex bridged by the first BNBN analogue of a butatriene is formed, as confirmed by structural and theoretical analyses. |
| Databáze: | OpenAIRE |
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