Bortolus Mark R, Mercier Hélène P A, Schrobilgen Gary J
Department of Chemistry, McMaster University, 1280 Main Street West, Hamilton, ON L8S 4M1, Canada.
Angew Chem Int Ed Engl. 2022 Nov 7;61(45):e202211699. doi: 10.1002/anie.202211699. Epub 2022 Oct 7.
The coordination complex, F XeF - - -WOF , was synthesized in CFCl solvent by reaction of the weak fluoride-ion donor and strong oxidative fluorinating agent, XeF , with the moderate-strength fluoride-ion acceptor, WOF . The compound is the only transition-metal coordination complex of Xe and was characterized at low temperatures by single-crystal X-ray diffraction and Raman spectroscopy. Xenon tetrafluoride and WOF coordinate trans to the W=O bond through a W- - -F bond. The XeF moiety of F XeF - - -WOF acquires a degree of [XeF ] character upon coordination that is reflected by its Xe-F stretching frequencies which are intermediate with respect to those of XeF and [XeF ] . Calculations show W- - -F is predominantly an electrostatic, σ-hole bond with a significant orbital contribution that accounts for the bent Xe-F - - -W angle. The calculations show F XeF - - -MOF (M=Cr, Mo) are less stable than their W analogue, consistent with failed attempts to synthesize F XeF - - -MoOF .
通过弱氟离子供体和强氧化性氟化剂XeF₂与中等强度氟离子受体WOF₄在CFCl₃溶剂中反应，合成了配位化合物F₅XeF⁻⁻WOF₄。该化合物是唯一的Xe的过渡金属配位化合物，并在低温下通过单晶X射线衍射和拉曼光谱进行了表征。四氟化氙和WOF₄通过W—F键与W=O键呈反式配位。F₅XeF⁻⁻WOF₄中的XeF₂部分在配位时获得了一定程度的[XeF₅]⁻特征，这通过其Xe—F伸缩频率得以体现，该频率相对于XeF₂和[XeF₅]⁻的频率处于中间值。计算表明W—F主要是一种静电σ-空穴键，具有显著的轨道贡献，这解释了弯曲的Xe—F⁻⁻W角度。计算表明F₅XeF⁻⁻MOF₄（M = Cr、Mo）比其W类似物稳定性更低，这与合成F₅XeF⁻⁻MoOF₄的尝试失败一致。
