Metathesis chemistry of inorganic cumulenes driven by B–O bond formation

IF 7.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Chemical Science Pub Date : 2024-12-18 DOI:10.1039/d4sc07487d
Jianqin Tang, Chenyang Hu, Agamemnon Crumpton, Liam Griffin, Jose M. Goicoechea, Simon Aldridge
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Abstract

The reaction chemistry of an unprecedented ‘inorganic cumulene’ - featuring a five-atom BNBNB chain - towards C=O (and related) multiple bonds is disclosed. In marked contrast to related all-carbon systems, the intrinsic polarity of the BNBNB chain (featuring electron-rich nitrogen and electron-deficient boron centres) enables metathesis chemistry with electrophilic heteroallenes such as CO2 and with organic carbonyl compounds. Transfer of the borylimide unit to [CO], [CS], [PP{(NDippCH2)2}] and [C(H)Ph] moieties generates (boryl)N=C=X systems (X = O, S, PP{(NDippCH2)2}, C(H)Ph), driven thermodynamically by B–O bond formation. Pairwise exchange of O and {(HCDippN)2}BN fragments occurs via consecutive [2+2] cyclo-addition/cyclo-reversion steps. An isolable complex of stoichiometry K[(boryl)NB(O)OC(H)Ph], formed via [2+2] cycloaddition to [(boryl)N=B=O]– can be shown to be an intermediate in the formation of (boryl)N=C(H)Ph, and provides corroborating evidence for a DFT-calculated mechanism proceeding via a ‘bora-Wittig’ mechanism.
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由 B-O 键形成驱动的无机积雪烯的复分解化学
本研究揭示了一种前所未有的 "无机积层烯"--具有五原子 BNBNB 链--与 C=O(及相关)多键的化学反应。与相关的全碳系统形成鲜明对比的是,BNBNB 链(以富电子的氮和缺电子的硼中心为特征)的固有极性使其能够与亲电杂烯烃(如 CO2)和有机羰基化合物发生偏合成化学反应。将硼酰亚胺单元转移到[CO]、[CS]、[PP{(NDippCH2)2}]和[C(H)Ph]分子上可生成 (boryl)N=C=X 系统(X = O、S、PP{(NDippCH2)2}、C(H)Ph),热力学上由 B-O 键的形成驱动。O 和 {(HCDippN)2}BN 片段通过连续的 [2+2] 环加成/环还原步骤进行成对交换。通过[(硼)N=B=O]-的[2+2]环加成形成的化学式为 K[(硼)NB(O)OC(H)Ph]的可分离复合物可以证明是形成(硼)N=C(H)Ph 的中间体,并为通过 "波拉-维蒂希 "机制进行的 DFT 计算机制提供了确凿的证据。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Chemical Science
Chemical Science CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
14.40
自引率
4.80%
发文量
1352
审稿时长
2.1 months
期刊介绍: Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.
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