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A New Cubane‐Type Ru 4 (CO) 12 (µ 3 ‐Se) 4 Tetramer Tailored for Water Photooxidation Catalysis
Author(s) -
Rupp Edgar,
Nowak Frank,
Fiechter Sebastian,
Reck Günter,
Eyert Volker,
AlonsoVante Nicolas,
Tributsch Helmut
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200109)2001:10<2489::aid-ejic2489>3.0.co;2-5
Subject(s) - chemistry , tetramer , cubane , catalysis , cluster (spacecraft) , combinatorial chemistry , crystallography , organic chemistry , crystal structure , enzyme , computer science , programming language
In an effort to tailor a transition metal complex for photoinduced water splitting, a new cubane‐like ruthenium chalcogenide tetramer, Ru 4 (CO) 12 (µ 3 ‐Se) 4 , has been synthesized and structurally characterized by single‐crystal X‐ray diffraction. The orange‐red compound crystallizes in the cubic space group I 4¯3 m . The geometry of the Ru 4 Se 4 units remains undistorted in the cubic symmetry 3 m . Such a high symmetry is exceptional among cubane‐type cluster compounds. Ruthenium atoms are octahedrally coordinated by three selenium atoms and three CO groups. Ru 4 Se 4 (CO) 12 clusters are linked via van der Waals forces by oxygen atoms which belong to CO ligands of two different cluster units. By stacking of the cluster units along the cubic axes two weakly coupled three‐dimensional frameworks are formed. First principles band structure calculations reveal the strong influence of both the C−O bonding, which leads to a large splitting into bonding and antibonding states, as well as of metal−ligand bonding. The latter gives rise to several very sharp Ru d bands of t 2g ‐like symmetry just below the valence band maximum E v , which are expected to be useful for oxidation catalysis. While these states are bonding below −1.3 eV, they are antibonding near the edge of the valence band. For this reason, we expect a stabilization of the cubane core on depopulation of the highest occupied bands. Consequently, it is likely that a dynamic interrelation between electron transfer and crystal structure occurs.