Jiang Shengjie, Cai Yanping, Carpentier Ambre, Del Rosal Iker, Maron Laurent, Xu Xin
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China.
LPCNO, CNRS & INSA, Université Paul Sabatier, 135 Avenue de Rangueil, 31077 Toulouse, France.
Inorg Chem. 2022 May 23;61(20):8083-8089. doi: 10.1021/acs.inorgchem.2c00956. Epub 2022 May 9.
This work provides a facile access to a series of triangular [ZnM] (M = group 10 and 11 metals) clusters. Treatment of Zn-Zn-bonded compounds [Zn-Zn] ( = CHC(2,6-PrCHN)CHC(CH)(NCHCHPR); R = Ph, Pr) with zero-valent transition-metal reagents selectively afforded the corresponding triangular clusters [ZnM], where M = Ni(0), Pd(0), and Pt(0). Notably, the isoelectronic triangular clusters [ZnM], where M = Ag(I) and Cu(I), could also be obtained by reactions of [LZn-ZnL] with AgOTf and CuOTf, respectively. The [ZnAg] complex containing elusive Zn-Ag bonds was investigated by density functional theory analysis, showing a 3c-2e bonding feature in the metallic ring. The electrochemical behaviors of [ZnM] complexes were examined and revealed the donation of electron density from the Zn-Zn σ-bond to the metal centers. Reaction of the [ZnNi] complex with isocyanide gave heterometallic species by coordination of isocyanide to the nickel center, keeping the trimetallic ring core structure intact. In contrast, the Zn-Zn bond was rapidly cleaved upon treatment of the [ZnNi] complex with dihydrogen or phenyl acetylene, generating the hydride- or acetylide-bridged heterotrimetallic complex.
这项工作提供了一种简便的方法来制备一系列三角形的[ZnM]（M = 第10族和第11族金属）簇合物。用零价过渡金属试剂处理锌-锌键合化合物[Zn-Zn]（ = CHC(2,6-PrCHN)CHC(CH)(NCHCHPR)；R = Ph，Pr）可选择性地得到相应的三角形簇合物[ZnM]，其中M = Ni(0)、Pd(0)和Pt(0)。值得注意的是，等电子三角形簇合物[ZnM]，其中M = Ag(I)和Cu(I)，也可分别通过[LZn-ZnL]与AgOTf和CuOTf的反应得到。通过密度泛函理论分析研究了含有难以捉摸的Zn-Ag键的[ZnAg]配合物，结果表明在金属环中存在3c-2e键合特征。研究了[ZnM]配合物的电化学行为，结果表明电子密度从Zn-Zn σ键向金属中心转移。[ZnNi]配合物与异腈反应，通过异腈与镍中心配位生成异金属物种，保持三金属环核心结构完整。相比之下，用氢气或苯乙炔处理[ZnNi]配合物时，Zn-Zn键迅速断裂，生成氢化物或乙炔化物桥连的异三金属配合物。
