Abstract
The coordination complex, F3 XeFb - - -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 F3 XeFb - - -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 F3 XeFb - - -MOF4 (M=Cr, Mo) are less stable than their W analogue, consistent with failed attempts to synthesize F3 XeFb - - -MoOF4 .
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