Syntheses, Structures, and Mössbauer Effect Spectroscopy of Triple-Decker Complexes Incorporating Nonamethylferrocene

详细信息    查看全文

• 作者：Andrew J. Schwartz ; Robert D. Pike ; Rolfe H. Herber ; Eric J. Watson
• 刊名：Organometallics
• 出版年：2016
• 出版时间：January 11, 2016
• 年：2016
• 卷：35
• 期：1
• 页码：62-69
• 全文大小：434K
• ISSN：1520-6041

文摘

Three new triple-decker complexes were synthesized by the reaction of nonamethylferrocene, Cp′FeCp* (Cp′ = C₅Me₄H, Cp* = C₅Me₅), with coordinatively unsaturated transition-metal complexes. The reaction of ruthenium cations [(C₅R₅)Ru]⁺ (R = H, Me) with Cp′FeCp* afforded the purple heterometallic triple-decker complexes [(C₅R₅)Ru(μ-Cp′)FeCp*]⁺ by electrophilic addition of ruthenium to the Cp′ ring of nonamethylferrocene. The analogous reaction with the manganese cation [Mn(CO)₃]⁺ produced the blue homometallic triple-decker complex [Cp*Fe(μ-Cp′)FeCp*]⁺ by abstraction of the Cp′ ring from Cp′FeCp* and subsequent addition of the newly generated cation [Cp*Fe]⁺ to 1 equiv of Cp′FeCp*. These experiments demonstrate that the asymmetry of Cp′FeCp* gives rise to a remarkable degree of regioselectivity such that ruthenium electrophiles add only to the Cp′ ring and never to the Cp* ring. In a similar way, [Mn(CO)₃]⁺ abstracts only the Cp′ ring from Cp′FeCp* to produce [Cp*Fe]⁺, which in turn adds only to the Cp′ ring of Cp′FeCp* to produce [Cp*Fe(μ-Cp′)FeCp*]⁺. Three air-stable triple-decker complexes incorporating nonamethylferrocene, [Cp*Fe(μ-Cp′)FeCp*]⁺ (1), [CpRu(μ-Cp′)FeCp*]⁺ (2), and [Cp*Ru(μ-Cp′)FeCp*]⁺ (3), have been characterized by NMR spectroscopy, elemental analysis, single-crystal X-ray diffraction analysis, and temperature-dependent ⁵⁷Fe M?ssbauer spectroscopy.