Aweke Bamlaku Semagne, Yu Cheng-Han, Shen Jiun-Shian, Wang Sheng, Yap Glenn P A, Chen Wen-Ching, Ong Tiow-Gan
Institute of Chemistry, Academia Sinica, Taipei 11529, Taiwan.
Department of Applied Chemistry, National Yang Ming Chiao Tung University, Hsinchu 30010, Taiwan.
Inorg Chem. 2023 Aug 14;62(32):12664-12673. doi: 10.1021/acs.inorgchem.3c00765. Epub 2023 Jul 31.
A facile synthesis of a binuclear Ag complex of a bis(carbone) ligand and its application as a carbone-transfer agent for the generation of other transition-metal complexes of Au (), Ni (), and Pd () is presented. Complex was synthesized through multiple synthetic routes under mild reaction conditions using the tetracationic [H][OTf·Cl] precursor salt, the dicationic [H][OTf] ylide salt, and the free ligand . The first two synthesis routes require no prior isolation of the air-, moisture-, and temperature-sensitive free ligand , thus affording complex with high yield and purity. Multinuclear NMR techniques, high-resolution mass spectrometry, and single-crystal X-ray diffraction analysis confirmed the identity of complex as a binuclear Ag complex of with a molecular formula of [Ag][OTf] and a 16-membered-ring metallomacrocyclic structure. During the transmetalation reaction with Au, the binuclear nature of complex remains intact to give analogous complex ([Au][OTf]). However, the dimeric structure was disrupted upon the carbone-transfer reaction with Ni and Pd, yielding mononuclear C-N-C pincer-type complexes ([NiCl][OTf]) and ([PdCl][OTf]), respectively. These results demonstrated the versatile use of complex as a carbone-transfer agent to other transition metals regardless of the type or size of the metals or the geometry they prefer.
本文介绍了一种双（碳烯）配体双核银配合物的简便合成方法及其作为碳烯转移剂用于生成金（）、镍（）和钯（）的其他过渡金属配合物的应用。配合物通过使用四阳离子[H][OTf·Cl]前体盐、二阳离子[H][OTf]叶立德盐和游离配体，在温和反应条件下通过多种合成路线合成。前两条合成路线无需事先分离对空气、水分和温度敏感的游离配体，从而以高收率和纯度得到配合物。多核核磁共振技术、高分辨率质谱和单晶X射线衍射分析证实配合物为配体的双核银配合物，分子式为[Ag][OTf]，具有16元环金属大环结构。在与金的金属转移反应中，配合物的双核性质保持完整，得到类似的配合物（[Au][OTf]）。然而，在与镍和钯的碳烯转移反应中，二聚体结构被破坏，分别生成单核C-N-C钳型配合物（[NiCl][OTf]）和（[PdCl][OTf]）。这些结果表明，配合物作为碳烯转移剂对其他过渡金属具有广泛的用途，而与金属的类型、大小或它们偏好的几何形状无关。
