State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, P. R. China.
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and, Department of Chemistry, College of Chemistry, and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China.
Chemistry. 2019 Nov 13;25(63):14295-14299. doi: 10.1002/chem.201904081. Epub 2019 Oct 17.
Frustrated Lewis pairs (FLPs) represent a new paradigm of main-group chemistry. The Lewis acidic centers in FLP chemistry are typically B and Al atoms in the studies reported over the past decade, and most of them are tri-coordinated with strong electron-withdrawing groups. Herein, a Ga/P system is reported which contains an unprecedented four-coordinated Lewis acidic Ga center. This Ga/P species performs classical addition reactions toward heterocumulenes, alkyne, diazomethane, and transition metal complex. Regioselective formation of the products can be rationalized by DFT calculations. The penta-coordinated gallium atom center in these products is rare in the FLP chemistry. This study enriches the diversity of FLPs and demonstrates that a four-coordinated Lewis acidic site with a donor-acceptor bond can also be FLP active.
受阻路易斯对（FLP）代表了主族化学的一种新范式。在过去十年的研究中，FLP 化学中的路易斯酸性中心通常是 B 和 Al 原子，它们大多数都与强吸电子基团三配位。本文报道了一个 Ga/P 体系，其中包含一个前所未有的四配位路易斯酸性 Ga 中心。该 Ga/P 物种对杂cumulenes、炔烃、重氮甲烷和过渡金属配合物进行经典加成反应。通过 DFT 计算可以合理地解释产物的区域选择性形成。这些产物中五配位的镓原子中心在 FLP 化学中很少见。本研究丰富了 FLP 的多样性，并证明了具有给体-受体键的四配位路易斯酸性位点也可以是 FLP 活性的。
