TY - JOUR
T1 - A square-planar tetracoordinate oxygen-containing Ti4O 17 cluster stabilized by two 1,1′-ferrocenedicarboxylato ligands
AU - Liu, Zhichang
AU - Lei, Juying
AU - Frasconi, Marco
AU - Li, Xiaohu
AU - Cao, Dennis
AU - Zhu, Zhixue
AU - Schneebeli, Severin T.
AU - Schatz, George C.
AU - Stoddart, J. Fraser
PY - 2014/8/25
Y1 - 2014/8/25
N2 - 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 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.
AB - 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 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.
KW - electrochemistry
KW - ferrocene
KW - oxido ligands
KW - titanium-oxo clusters
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U2 - 10.1002/anie.201402603
DO - 10.1002/anie.201402603
M3 - Article
C2 - 24990809
VL - 53
SP - 9193
EP - 9197
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 35
ER -