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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.

Authors

J.D. Farmer

R.L. Roberts

M.I. Humphrey

P.J. Low



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