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A Square‐Planar Tetracoordinate Oxygen‐Containing Ti 4 O 17 Cluster Stabilized by Two 1,1′‐Ferrocenedicarboxylato Ligands
Author(s) -
Liu Zhichang,
Lei Juying,
Frasconi Marco,
Li Xiaohu,
Cao Dennis,
Zhu Zhixue,
Schneebeli Severin T.,
Schatz George C.,
Stoddart J. Fraser
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201402603
Subject(s) - tetracoordinate , cluster (spacecraft) , chemistry , crystallography , octahedron , atomic orbital , molecular orbital , planar , steric effects , titanium , tetramer , oxygen , ferrocene , molecule , electrochemistry , electron , stereochemistry , crystal structure , physics , electrode , biochemistry , computer graphics (images) , enzyme , organic chemistry , quantum mechanics , computer science , programming language
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 [{Ti 4 (μ 4 ‐O)(μ 2 ‐O) 2 }(OPr i ) 6 (fdc) 2 ], which possesses a unique edge‐sharing Ti 4 O 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’t Hoff/Le Bel oxygen, which has been probed by theoretical calculations, can be described by two horizontally σ‐bonded 2p x and 2p y orbitals along with one perpendicular nonbonded 2p z 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.