Noninnocent Ligand Behavior in Diruthenium Complexes Containing a 1,3-Diethynylbenzene Bridge

M.A. Fox, J.D. Farmer, R.L. Roberts, M.G. Humphrey, Paul Low

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Abstract

The electronic structures of 1,3-{trans-Cl(dppe)2RuC≡C}2C6H4 (3) and 1,3-{Cp*(dppe)RuC≡C}2C6H4 (4) in their available redox states have been investigated using a combination of UV−vis−near-IR and IR spectroscopy and computational methods. In contrast to the case for closely related iron compounds, for the ruthenium complexes 3 and 4 the bridging aryl moiety is heavily involved in the oxidation process, and consequently descriptions of the electronic structures and electronic transitions in terms of the language developed for mixed-valence systems with clearly identifiable metal oxidation states are not appropriate. Consequently, the unique low-energy (near-IR) absorption bands observed for the asymmetric cations [3]+ and [4]+ are better described as arising from charge transfer transitions from a metal acetylide donor to a metal phenylacetylide acceptor rather than in terms of IVCT transitions.
Original languageEnglish
Pages (from-to)5266 - 5269
JournalOrganometallics
Volume28
Issue number17
Early online date10 Aug 2009
DOIs
Publication statusPublished - 14 Sep 2009

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