The Organozinc Rich Compounds [Cp*M(ZnR)5] (M = Fe, Ru; R = Cp*, Me, Cl, Br)

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• 作者：Mariusz Molon ; Christian Gemel ; R眉diger W. Seidel ; Paul Jerabek ; Gernot Frenking ; Roland A. Fischer
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：June 17, 2013
• 年：2013
• 卷：52
• 期：12
• 页码：7152-7160
• 全文大小：394K
• 年卷期：v.52,no.12(June 17, 2013)
• ISSN：1520-510X

文摘

Organozinc (ZnR with R = Cp*, Me, Cl, Br) ligated transition metal (M) half-sandwich compounds of general formula [Cp*M(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 [{Cp*Ru(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, ¹H and ¹³C NMR spectroscopy as well as by single crystal X-ray diffraction techniques, if applicable. The coordination polyhedra of [Cp*M(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*.