期刊
CHEMICAL RECORD
卷 4, 期 5, 页码 279-290出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/tcr.20021
关键词
redox interaction; mixed-valence state; metal-cluster complex; electro n -transfer; oxo-centered triruthenium complex
The ligand-ligand redox interaction separated by di-, tri-, and hexanuclear Cluster units is discussed in terms of the splitting of the redox waves (AEa((L))) and the comproportionation constants of the ligand-based mixed valence state. Although two redox-active monodentate ligands in the rnononuclear ruthenium(II) complexes (either cis or trans configurations) do not show appreciable splitting in their reduction waves, interestingly those separated by giant triruthenium and hexarhenium Cluster units clearly show splitting. The molecular orbital considerations in the literature suggest that these units possess some pi-type molecular orbitals composed of metal dpi and possibly ligand ppi orbitals. Absence of the redox interactions in oxo-bridged diruthenium(II) and oxo-centered trirliodium(III) complexes where such pi molecular orbitals (including an antibonding one) are fully occupied, indicates the importance of empty pi* orbitals for the ligand redox communication. (C) 2004 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.
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