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Hoffmann, R. A wiki for the life sciences where authorship matters. Nature Genetics (2008)
 

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Characterization of the low-energy electronic excited states of benzoyl-substituted ruthenocenes.

Electronic absorption and resonance Raman spectral studies of benzoylruthenocene (BRc) and 1,1'-dibenzoylruthenocene (DRc) indicate that the low-energy electronic excited states of these 4d(6) metallocenes possess metal-to-ligand charge transfer (MLCT) character. While this MLCT contribution should weaken the metal-ring bonding in the excited state, neither compound is photosensitive in nonhalogenated solvents such as methanol, acetonitrile, and cyclohexane. In contrast, irradiating BRc and DRc in the good electron-accepting solvent, carbon tetrachloride, results in ring loss via a pathway that appears to originate from a charge-transfer-to-solvent excited state. Both metallocenes function as photoinitiators for the anionic polymerization of ethyl 2-cyanoacrylate, and the kinetics and mechanism of this process have been investigated. Comparing the present results on BRc and DRc with those reported earlier for the corresponding benzoyl-substituted ferrocene compounds reveals some interesting commonalities and differences between the excited-state properties of these 3d and 4d metallocenes.[1]

References

  1. Characterization of the low-energy electronic excited states of benzoyl-substituted ruthenocenes. Sanderson, C.T., Quinlan, J.A., Conover, R.C., Johnson, M.K., Murphy, M., Dluhy, R.A., Kutal, C. Inorganic chemistry. (2005) [Pubmed]
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