Ionic-Liquid-Based Synthesis of the Germanium-Iron Carbonyls FeI₄{GeI₃Fe(CO)₃}₂ and (GeI₃)₂Fe(CO)₄

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• 作者：Silke Wolf and Claus Feldmann
• 刊名：Zeitschrift für anorganische und allgemeine Chemie
• 出版年：2017
• 出版时间：January 2017
• 年：2017
• 卷：643
• 期：1
• 页码：25-30
• 全文大小：798K
• ISSN：1521-3749

文摘

Dark red and brick red transparent crystals of FeI₄{GeI₃Fe(CO)₃}₂ (1) and (GeI₃)₂Fe(CO)₄ (2) were obtained by reacting GeI₄ and Fe₂(CO)₉ or Fe₃(CO)₁₂ in a mixture of [BMIM]Cl and AlCl₃ as ionic liquid (BMIm = 1-butyl-3-methylimidazolium). According to X-ray structure analysis based on single crystals, the title compounds exhibit cluster units with Fe–Ge bonds. FeI₄{GeI₃Fe(CO)₃}₂ consists of two GeI₂I_1/2-Fe(CO)₃I_2/2 units that are interlinked by a distorted octahedral FeI_6/2 group. (GeI₃)₂Fe(CO)₄ consists of two GeI₃ units that are connected by a square planar Fe(CO)₄ group with a linear Ge–Fe–Ge unit. Depending on the synthesis conditions, interestingly, (GeI₃)₂Fe(CO)₄ crystallizes either in P2₁/n (2a) or in Plass="">1 (2b). 2a exhibits a more dense packing, whereas 2b exhibits shorter intermolecular I–I distances. Both title compounds are temperature labile and highly sensitive to oxygen, moisture and illumination, including X-ray irradiation. They decompose with release of CO in absence of certain CO atmosphere. In addition to crystal structure analysis the compounds were characterized by energy dispersive X-ray (EDX) analysis, thermogravimetry (TG) and infrared spectroscopy (FT-IR).