Homoleptic tetranuclear complexes of divalent tin and lead tetraolates, M4(hfpt)2 (hfpt4- is an anion of 1,1,1,5,5,5-hexafluoropentane-2,2,4,4-tetraol), have been obtained in high yield from the corresponding (trimethylsilyl)amides. The solid-state structures of compounds contain discrete molecules in which a butterfly tetrahedron of metal atoms is sandwiched between two tetraolate ligands acting in tetradentate mode. The lone-pair Sn2+ and Pb2+ cations were found to exhibit pyramidal coordination of four ligand oxygen atoms. The retention of polynuclear structure in solution was unambiguously confirmed by multinuclear NMR spectroscopy. An interesting example of the strong through-space coupling between 19F of the tetraolate trifluoromethyl groups and 117/119Sn or 207Pb nuclei was discovered. Both compounds were shown to have clean, low-temperature decomposition in air that results in phase-pure oxides SnO2 and PbO, respectively. Thermal decomposition studies revealed a great potential of metal tetraolate complexes as prospective molecular precursors for the soft chemistry approach to metal oxides.

Homoleptic tetraolates of tin and lead

244th National Meeting (2012)

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