Department of Inorganic Chemistry II-Organometallics & Materials, Ruhr University Bochum, 44780 Bochum, Germany.
Inorg Chem. 2013 Jun 17;52(12):7152-60. doi: 10.1021/ic400741b. Epub 2013 May 23.
Organozinc (ZnR with R = Cp*, Me, Cl, Br) ligated transition metal (M) half-sandwich compounds of general formula [CpM(ZnR)5] (M = Fe, Ru) are presented in this work. The new compounds were obtained by treatment of various GaCp ligated precursors with suitable amounts of ZnMe2 to exchange Ga against Zn. This exchange follows a strict Ga:Zn ratio of 1:2. Accordingly, a Ga/Zn mixed compound [{CpRu(GaCp)(ZnCp*)(ZnCl)2}2] can be obtained if the amount of ZnMe2 is reduced so that one GaCp* remains coordinated to the transition metal. All new compounds were characterized by elemental analysis, (1)H and (13)C NMR spectroscopy as well as by single crystal X-ray diffraction techniques, if applicable. The coordination polyhedra of [CpM(ZnR)5] can be derived from the pseudo homoleptic parent compound [Ru(ZnCp)4(ZnMe)6], as emphasized by continuous shape measures analysis (CShM). Computational investigations at the density functional theory (DFT) level of theory were performed, revealing no significant attractive interaction of the zinc atoms and therefore these compounds are best described as classical complexes, rather than cluster compounds. The Ru-L bond strength follow the order Cp* > ZnCl > ZnMe > ZnCp*.
本文介绍了通式为[CpM(ZnR)5]（M = Fe, Ru）的有机锌（ZnR，R = Cp，Me，Cl，Br）配位的过渡金属半夹心化合物。这些新化合物是通过用适量的 ZnMe2处理各种 GaCp配位前体制得的，用 Zn 取代 Ga。这种取代遵循严格的 Ga:Zn 摩尔比为 1:2。因此，如果减少 ZnMe2 的用量，使一个 GaCp仍然与过渡金属配位，就可以得到 Ga/Zn 混合化合物[{CpRu(GaCp)(ZnCp*)(ZnCl)2}2]。所有新化合物均通过元素分析、(1)H 和(13)C NMR 光谱以及单晶 X 射线衍射技术进行了表征，如果适用的话。[CpM(ZnR)5]的配位多面体可以由假同核母体化合物[Ru(ZnCp)4(ZnMe)6]推导出来，正如连续形状度量分析（CShM）所强调的那样。在密度泛函理论（DFT）水平上进行了计算研究，结果表明锌原子之间没有明显的吸引力相互作用，因此这些化合物最好被描述为经典配合物，而不是簇合物。Ru-L 键强度的顺序为 Cp* > ZnCl > ZnMe > ZnCp*。
