A square-planar tetracoordinate oxygen-containing Ti4O 17 cluster stabilized by two 1,1′-ferrocenedicarboxylato ligands

Zhichang Liu, Juying Lei, Marco Frasconi, Xiaohu Li, Dennis Cao, Zhixue Zhu, Severin T. Schneebeli, George C. Schatz, J. Fraser Stoddart

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24 Citations (Scopus)

Abstract

By introducing steric constraints into molecular compounds, it is possible to achieve atypical coordination geometries for the elements. Herein, we demonstrate that a titanium-oxo cluster [{Ti44-O) (μ2-O)2}(OPri)6(fdc) 2], which possesses a unique edge-sharing Ti4O 17 octahedron tetramer core, is stabilized by the constraints produced by two orthogonal 1,1′-ferrocenedicarboxylato (fdc) ligands. As a result, a square-planar tetracoordinate oxygen (ptO) can be generated. The bonding pattern of this unusual anti-van'tHoff/LeBel oxygen, which has been probed by theoretical calculations, can be described by two horizontally σ-bonded 2px and 2py orbitals along with one perpendicular nonbonded 2pz orbital. While the two ferrocene units are separated spatially by the ptO with an Fe⋯Fe separation of 10.4Å, electronic communication between them still takes place as revealed by the cluster's two distinct one-electron electrochemical oxidation processes. A square-planar tetracoordinate oxygen (ptO) is realized in an edge-sharing Ti4O17 octahedron tetramer stabilized by two orthogonal 1,1′-ferrocenedicarboxylato ligands. Whereas the two ferrocene units are separated spatially by the ptO with an Fe⋯Fe separation of 10.4Å, the electronic communication between them still takes place as indicated by the cluster's two distinct one-electron electrochemical oxidation processes.

Original languageEnglish
Pages (from-to)9193-9197
Number of pages5
JournalAngewandte Chemie - International Edition
Volume53
Issue number35
DOIs
Publication statusPublished - Aug 25 2014

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Keywords

  • electrochemistry
  • ferrocene
  • oxido ligands
  • titanium-oxo clusters

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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