铂模板化的B=N单元偶联反应：1,3 - 二烯和丁三烯的BNBN类似物的合成
Platinum-Templated Coupling of B=N Units: Synthesis of BNBN Analogues of 1,3-Dienes and a Butatriene.
作者信息
Brunecker Carina, Arrowsmith Merle, Fantuzzi Felipe, Braunschweig Holger
机构信息
Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
出版信息
Angew Chem Int Ed Engl. 2021 Jul 26;60(31):16864-16868. doi: 10.1002/anie.202106161. Epub 2021 Jun 24.
The 1:2 reaction of [μ-(dmpm)Pt(nbe)] (dmpm=bis(dimethylphosphino)methane, nbe=norbornene) with Cl BNR(SiMe ) (R=tBu, SiMe ) yields unsymmetrical (N-aminoboryl)aminoboryl Pt complexes by B-N coupling via ClSiMe elimination. A subsequent intramolecular ClSiMe 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 BN(SiMe ) leads, via a twofold BrSiMe elimination, to a Pt A-frame complex bridged by a linear BNBN isostere of butatriene. Structural and computational data confirm π electron delocalization over the entire BNBN unit.
[μ-(二甲基膦亚甲基)铂(降冰片烯)]（dmpm = 双(二甲基膦基)甲烷，nbe = 降冰片烯）与Cl BNR(SiMe )（R = tBu，SiMe ）按1:2反应，通过消除ClSiMe 经B-N偶联生成不对称的(氨基硼基)氨基硼基铂 配合物。随后从叔丁基衍生物中进行分子内ClSiMe 消除导致BNBN单元环化，形成独特的1,3,2,4-二氮杂二硼杂环丁烷-2-基配体。相比之下，与Br BN(SiMe )的类似反应通过两次消除BrSiMe ，生成由丁三烯的线性BNBN等电子体桥连的铂 A 型配合物。结构和计算数据证实了整个BNBN单元上的π电子离域。
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