Abstract
Most high and medium oxidation state (O.S. ≥ 3) metal and non-metal fluorides and oxide fluorides have Lewis acidic properties, although detailed exploration of their chemistry with neutral ligands, which differs significantly from that with chloride, bromide or iodide co-ligands, has only been undertaken in recent years. The previous review (Benjamin et. al. Chem. Soc. Rev. 42 (2013) 1460) covered work published up to ∼2011, and the present article covers new work up to early 2019, a period which has seen many new contributions to the field. This article describes work on the coordination chemistry of d, f and p-block fluorides and oxide fluorides with neutral ligands containing donor atoms drawn from Groups 15 (N, P, As or Sb) and 16 (O, S, Se or Te) and including N-heterocyclic carbenes. The incorporation of the radionuclide 18F into neutral metal complexes and their use in medical diagnosis via positron emission tomography (PET) is also described, along with briefer coverage of other potential applications.
Highlights
Introduction and ScopeThe coordination chemistry of metal fluorides and oxide fluorides has traditionally developed separately from that of the heavier halides, and, until the last twenty-five years, the characterisation of the complexes was often poor and the properties were not investigated in any detail [1,2]
Over the approximately eight years covered by this article, there have been many advances in the coordination chemistry of metal fluorides, including the first N-base complexes of AuF3, phosphine and arsine complexes of the highest oxidation states of the heavy group 5 and 6 elements, NbF5, TaF5 and WF6, and an impressive number of carbene (NHC) complexes with many element fluorides across the Periodic Table
Whilst lanthanide chemistry remains very limited, the chemistry of uranium fluoride complexes is developing, and there are sufficient examples to indicate that a substantial coordination chemistry with N- and O-donor ligands will exist for Pa, U, Np, Pu and Am, the need for high level radioactivity facilities obviously greatly limits work on the post-uranium elements
Summary
The coordination chemistry of metal fluorides and oxide fluorides has traditionally developed separately from that of the heavier halides, and, until the last twenty-five years, the characterisation of the complexes was often poor and the properties were not investigated in any detail [1,2]. In a review published in 2013 [7], we discussed the chemistry of metal and non-metal fluoride and oxide fluoride complexes containing neutral donor ligands with the metal/non-metal Lewis acid in oxidation states ≥ 3. Complexes in the higher oxidation states demonstrate the very significant differences imposed by the fluoride ligands on the metal/non-metal centre and result in quite different stabilities and reactivities compared to complexes containing the heavier halides, alkoxides, amides, etc. Other recent reviews covering aspects of fluorine chemistry are: Crystal Chemistry and Selected Physical Properties of Inorganic Fluorides and OxideFluorides [17]; Molecular Hexafluorides [18]; A survey of titanium fluoride complexes, their preparation, reactivity and applications [14]; and Highly reactive carbenes as ligands for main group element fluorides [19]. Reviews covering relevant aspects of the chemistry of single elements are listed in the appropriate sections below
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