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Platinum‐Templated Coupling of B=N Units: Synthesis of BNBN Analogues of 1,3‐Dienes and a Butatriene
Author(s) -
Brunecker Carina,
Arrowsmith Merle,
Fantuzzi Felipe,
Braunschweig Holger
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202106161
Subject(s) - chemistry , intramolecular force , platinum , coupling reaction , norbornene , derivative (finance) , delocalized electron , medicinal chemistry , ligand (biochemistry) , stereochemistry , catalysis , organic chemistry , polymer , monomer , financial economics , economics , biochemistry , receptor
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.