A Square‐Planar Tetracoordinate Oxygen‐Containing Ti4O17 Cluster Stabilized by Two 1,1′‐Ferrocenedicarboxylato Ligands |
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| Authors: | Dr Zhichang Liu Juying Lei Dr Marco Frasconi Dr Xiaohu Li Dennis Cao Dr Zhixue Zhu Dr Severin T Schneebeli Prof George C Schatz Prof J Fraser Stoddart |
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| Institution: | 1. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208 (USA) http://stoddart.northwestern.edu;2. Present address: School of Resources and Environmental Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237 (China);3. Present address: Combustion Research Facility, Sandia National Laboratories, Livermore, CA 94550 (USA) |
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| 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 {Ti4(μ4‐O)(μ2‐O)2}(OPri)6(fdc)2], which possesses a unique edge‐sharing Ti4O17 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’t Hoff/Le Bel 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 10.4 Å, electronic communication between them still takes place as revealed by the cluster’s two distinct one‐electron electrochemical oxidation processes. |
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| Keywords: | electrochemistry ferrocene oxido ligands titanium‐oxo clusters |
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