Synthesis, Structure, and Bonding of a XeIV Transition‐Metal Coordination Complex, F3XeFb‐ ‐ ‐WOF4Journal Articles
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AbstractThe coordination complex, F3XeFb‐ ‐ ‐WOF4, was synthesized in CFCl3 solvent by reaction of the weak fluoride‐ion donor and strong oxidative fluorinating agent, XeF4, with the moderate‐strength fluoride‐ion acceptor, WOF4. The compound is the only transition‐metal coordination complex of XeIV and was characterized at low temperatures by single‐crystal X‐ray diffraction and Raman spectroscopy. Xenon tetrafluoride and WOF4 coordinate trans to the W=O bond through a W‐ ‐ ‐Fb bond. The XeF3 moiety of F3XeFb‐ ‐ ‐WOF4 acquires a degree of [XeF3]+ character upon coordination that is reflected by its Xe−F stretching frequencies which are intermediate with respect to those of XeF4 and [XeF3]+. Calculations show W‐ ‐ ‐Fb is predominantly an electrostatic, σ‐hole bond with a significant orbital contribution that accounts for the bent Xe−Fb‐ ‐ ‐W angle. The calculations show F3XeFb‐ ‐ ‐MOF4 (M=Cr, Mo) are less stable than their W analogue, consistent with failed attempts to synthesize F3XeFb‐ ‐ ‐MoOF4.
