Ruthenium complexes with non-innocent ligands: Electron distribution and implications for catalysis

Julie L. Boyer, Jonathan Rochford, Ming Kang Tsai, James T. Muckerman, Etsuko Fujita*


研究成果: 雜誌貢獻回顧評介論文同行評審

145 引文 斯高帕斯(Scopus)


Ruthenium complexes with the non-innocent ligands (NILs) benzoquinone, iminobenzoquinone and benzoquinonediimine and their redox derivatives exhibit intriguing electronic properties. With the proper ligand set the NIL π* orbitals mix extensively with the ruthenium dπ orbitals resulting in delocalized electron distributions and non-integer oxidation states, and in most of these systems a particular ruthenium oxidation state dominates. This review critically examines the electronic structure of Ru-NIL systems from both an experimental and computational (DFT) perspective. The electron distribution within these complexes can be modulated by altering both the ancillary ligands and the NIL, and in a few cases the resultant electron distributions are exploited for catalysis. The Ru-NIL systems that perform alcohol oxidation and water oxidation catalysis are discussed in detail. The Tanaka catalyst, an anthracene-bridged dinuclear Ru complex, is an intriguing example of a Ru-NIL framework in catalysis. Unlike other known ruthenium water oxidation catalysts, the two Ru atoms remain low valent during the catalytic cycle according to DFT calculations, some experimental evidence, and predictions based on the behavior of the related mononuclear species.

頁(從 - 到)309-330
期刊Coordination Chemistry Reviews
出版狀態已發佈 - 2010 2月

ASJC Scopus subject areas

  • 物理與理論化學
  • 無機化學
  • 材料化學


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