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

Fox, M.A.; Farmer, J.D.; Roberts, R.L.; Humphrey, M.I.; Low, P.J.

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.

Citation

Fox, M., Farmer, J., Roberts, R., Humphrey, M., & Low, P. (2009). Noninnocent Ligand Behavior in Diruthenium Complexes Containing a 1,3-Diethynylbenzene Bridge. Organometallics, 28(17), 5266-5269. https://doi.org/10.1021/om900200n

• Journal Article Type: Article
• Online Publication Date: Aug 10, 2009
• Publication Date: 2009-09
• Deposit Date: Apr 30, 2012
• Journal: Organometallics
• Print ISSN: 0276-7333
• Electronic ISSN: 1520-6041
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 28
• Issue: 17
• Pages: 5266-5269
• DOI: https://doi.org/10.1021/om900200n
• Public URL: https://durham-repository.worktribe.com/output/1476222