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The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique
Published on: November 28, 2016
Homoleptic tetranuclear complexes of divalent tin and lead tetraolates
Zheng Wei1, Jen-Hsien Yang, Volodimir D Vreshch
1Department of Chemistry, University at Albany, SUNY, Albany, New York 12222, USA.
Abstract:
Homoleptic tetranuclear complexes of divalent tin and lead tetraolates, M(4)(hfpt)(2) [M = Sn (1) and Pb (2); hfpt(4-) 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 1 and 2 contain discrete molecules in which a butterfly tetrahedron of metal atoms is sandwiched between two tetraolate ligands acting in tetradentate mode. The lone-pair Sn(2+) and Pb(2+) cations exhibit pyramidal coordination of four ligand oxygen atoms. A multinuclear NMR study unambiguously confirmed that metal tetraolates retain their polynuclear structure in solution of even coordinating solvents. An interesting example of the strong through-space coupling between (19)F of the tetraolate trifluoromethyl groups and (117/119)Sn or (207)Pb nuclei was found. Both compounds were shown to have clean, low-temperature decomposition that results in crystalline oxides SnO(2) and PbO, respectively, for 1 and 2. This work demonstrates the remarkable coordination properties of the tetraolate ligand that can be utilized for the preparation of a wide variety of poly- and heterometallic complexes. Decomposition studies revealed a great potential of metal tetraolate complexes as prospective molecular precursors for the soft chemistry approach to oxide materials.
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