Synthesis, Structure, and Bonding of a XeIV Transition‐Metal Coordination Complex, F3XeFb‐ ‐ ‐WOF4

Abstract The coordination complex, F 3 XeF b ‐ ‐ ‐WOF 4 , was synthesized in CFCl 3 solvent by reaction of the weak fluoride‐ion donor and strong oxidative fluorinating agent, XeF 4 , with the moderate‐strength fluoride‐ion acceptor, WOF 4 . The compound is the only transition‐metal coordination complex of Xe IV and was characterized at low temperatures by single‐crystal X‐ray diffraction and Raman spectroscopy. Xenon tetrafluoride and WOF 4 coordinate trans to the W=O bond through a W‐ ‐ ‐F b bond. The XeF 3 moiety of F 3 XeF b ‐ ‐ ‐WOF 4 acquires a degree of [XeF 3 ] + character upon coordination that is reflected by its Xe−F stretching frequencies which are intermediate with respect to those of XeF 4 and [XeF 3 ] + . Calculations show W‐ ‐ ‐F b is predominantly an electrostatic, σ‐hole bond with a significant orbital contribution that accounts for the bent Xe−F b ‐ ‐ ‐W angle. The calculations show F 3 XeF b ‐ ‐ ‐MOF 4 (M=Cr, Mo) are less stable than their W analogue, consistent with failed attempts to synthesize F 3 XeF b ‐ ‐ ‐MoOF 4 .