XeF<sub>4</sub> as a Ligand for a Metal Ion

Tavčar, Gašper; Žemva, Boris

doi:10.1002/ange.200803365

Angewandte Chemie

2009

DOI: 10.1002/ange.200803365

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XeF₄ as a Ligand for a Metal Ion

Gašper Tavčar

Boris Žemva

Abstract: Edles Molekül: [Mg(XeF2)(XeF4)](AsF6)2 ist die erste Koordinationsverbindung, in der XeF4 als an ein Metallzentrum gebundener Ligand vorliegt. Es ist auch die erste bekannte Verbindung, in der XeF2 und XeF4 gemeinsam an dasselbe Metallzentrum binden (siehe Struktur; lila Xe, grün F, grau Mg, gelb As).

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Coordination of KrF₂ to a Naked Metal Cation, Mg²⁺

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Examples of coordination compounds in which KrF2 functions as a ligand are very rare. In contrast, XeF2 provides a rich coordination chemistry with a variety of main‐group and transition metal cations. The reactions of Mg(AsF6)2 and KrF2 in HF or BrF5 solvent have afforded [Mg(KrF2)4(AsF6)2] and [Mg(KrF2)4(AsF6)2]⋅2 BrF5, respectively, the first examples of a metal cation ligated by KrF2. Their X‐ray crystal structures and Raman spectra show that the KrF2 ligands and [AsF6]− anions are F‐coordinated to a naked Mg2+ cation. Quantum‐chemical calculations are consistent with essentially non‐covalent ligand‐metal bonding. These compounds significantly extend the XeF2–KrF2 analogy and the limited chemistry of krypton by introducing a new class of coordination compound in which KrF2 functions as a ligand towards a naked metal cation.

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Coordination of KrF₂ to a Naked Metal Cation, Mg²⁺

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Synthesis, Structure, and Bonding of a Xe^IV Transition‐Metal Coordination Complex, F₃XeF_b‐ ‐ ‐WOF₄

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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 transitionmetal 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 XeÀ 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 XeÀ 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 .

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Coordination of KrF₂ to a Naked Metal Cation, Mg²⁺

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Examples of coordination compounds in which KrF functions as a ligand are very rare. In contrast, XeF provides a rich coordination chemistry with a variety of main-group and transition metal cations. The reactions of Mg(AsF ) and KrF in HF or BrF solvent have afforded [Mg(KrF ) (AsF ) ] and [Mg(KrF ) (AsF ) ]⋅2 BrF , respectively, the first examples of a metal cation ligated by KrF . Their X-ray crystal structures and Raman spectra show that the KrF ligands and [AsF ] anions are F-coordinated to a naked Mg cation. Quantum-chemical calculations are consistent with essentially non-covalent ligand-metal bonding. These compounds significantly extend the XeF -KrF analogy and the limited chemistry of krypton by introducing a new class of coordination compound in which KrF functions as a ligand towards a naked metal cation.

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XeF₄ as a Ligand for a Metal Ion

Cited by 4 publications

References 16 publications

Coordination of KrF₂ to a Naked Metal Cation, Mg²⁺

Coordination of KrF₂ to a Naked Metal Cation, Mg²⁺

Synthesis, Structure, and Bonding of a Xe^IV Transition‐Metal Coordination Complex, F₃XeF_b‐ ‐ ‐WOF₄

Coordination of KrF₂ to a Naked Metal Cation, Mg²⁺

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XeF4 as a Ligand for a Metal Ion

Cited by 4 publications

References 16 publications

Coordination of KrF2 to a Naked Metal Cation, Mg2+

Coordination of KrF2 to a Naked Metal Cation, Mg2+

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

Coordination of KrF2 to a Naked Metal Cation, Mg2+

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XeF₄ as a Ligand for a Metal Ion

Coordination of KrF₂ to a Naked Metal Cation, Mg²⁺

Coordination of KrF₂ to a Naked Metal Cation, Mg²⁺

Synthesis, Structure, and Bonding of a Xe^IV Transition‐Metal Coordination Complex, F₃XeF_b‐ ‐ ‐WOF₄

Coordination of KrF₂ to a Naked Metal Cation, Mg²⁺