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

ABSTRACT: The 1:2 reaction of [μ-(dmpm)Pt(nbe)]₂ (dmpm=bis(dimethylphosphino)methane, nbe=norbornene) with Cl₂ BNR(SiMe₃ ) (R=tBu, SiMe₃ ) yields unsymmetrical (N-aminoboryl)aminoboryl Pt^I 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 Br₂ BN(SiMe₃ )₂ leads, via a twofold BrSiMe₃ 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.

SUBMITTER: Brunecker C

PROVIDER: S-EPMC8362192 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature

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

Brunecker Carina C Arrowsmith Merle M Fantuzzi Felipe F Braunschweig Holger H

Angewandte Chemie (International ed. in English) 20210624 31

The 1:2 reaction of [μ-(dmpm)Pt(nbe)]2 (dmpm=bis(dimethylphosphino)methane, nbe=norbornene) with Cl2 BNR(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, t ...[more]

PMID: 34036694

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