Octafluorodirhenate(III) Revisited: Solid-State Preparation, Characterization, and Multiconfigurational Quantum Chemical Calculations

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• 作者：Samundeeswari Mariappan Balasekaran ; Tanya K. Todorova ; Chien Thang Pham ; Thomas Hartmann ; Ulrich Abram ; Alfred P. Sattelberger ; Frederic Poineau
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：June 6, 2016
• 年：2016
• 卷：55
• 期：11
• 页码：5417-5421
• 全文大小：293K
• 年卷期：0
• ISSN：1520-510X

文摘

A simple method for the high-yield preparation of (NH₄)₂[Re₂F₈]·2H₂O has been developed that involves the reaction of (n-Bu₄N)₂[Re₂Cl₈] with molten ammonium bifluoride (NH₄HF₂). Using this method, the new salt [NH₄]₂[Re₂F₈]·2H₂O was prepared in ∼90% yield. The product was characterized in solution by ultraviolet–visible light (UV-vis) and ¹⁹F nuclear magnetic resonance (¹⁹F NMR) spectroscopies and in the solid-state by elemental analysis, powder X-ray diffraction (XRD), and infrared (IR) spectroscopy. Multiconfigurational CASSCF/CASPT2 quantum chemical calculations were performed to investigate the molecular and electronic structure, as well as the electronic absorption spectrum of the [Re₂F₈]^2– anion. The metal–metal bonding in the Re₂⁶⁺ unit was quantified in terms of effective bond order (EBO) and compared to that of its [Re₂Cl₈]^2– and [Re₂Br₈]^2– analogues.