Bi- and monometallic trifluoroacetates have the potential to serve as fluorinated precursors for the low-temperature synthesis of optical fluoride materials. Solid-state thermolysis of trifluoroacetates involves conversion of a metal–organic network into a fully inorganic material with three-dimensional connectivity given by metal–fluorine–metal bridges. No efforts have been made thus far to establish the mechanistic aspects of this solid-state transformation. Specifically, no intermediates have been identified. One of the main deterrents to undertake this study is the challenge of obtaining single crystals with enough quality for X-ray diffraction.<br/> <br/>In this talk I will describe the first attempts to probe intermediates occurring during the solid-state thermolysis of bi- and monometallic trifluoroacetates. Decomposition rates are controlled carefully in order to get crystals large enough for structure elucidation. Special emphasis is placed on identifying intermediates in which both organofluorine and fluoride are directly coordinated to the metal atoms, as this may depict the first step towards the formation of mixed-metal fluorides starting from organic–inorganic fluorinated hybrids. Two intermediates are identified and structurally characterized. These feature uncommon geometries in which fluoride ions bridge 3 and 4 metal atoms in trigonal planar and square planar geometries. An additional outcome of these reactivity studies is the demonstration that trifluoroacetates serve as a mild fluorinating agent for the low-temperature (&lt;400 °C) synthesis of technologically relevant optical fluorides.

Solid-state reactivity of metal trifluoroacetates

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