Diruthenium Naphthalene and Anthracene Complexes Containing a Doubly Linked Dicyclopentadienyl Ligand
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abstract
The reaction of cis-{( 5-C 5H 3) 2(CMe 2) 2}Ru 2(CO) 4Br 2 with naphthalene affords the syn-facial [cis-{( 5- C 5H 3) 2(CMe 2) 2}Ru 2(- 6, 6-C 10H 8)][OTf] 2, (2 2+), a complex that appears to be two electrons short of the 18-electron rule. Density functional theory (DFT) calculations suggest that the Ru atoms satisfy their missing valence by a combination of a weak metal-metal bond and sharing electrons from the central bond of the naphthalene. The one-electron reduction of 2 2+ yields 2 +, a Class II mixed-valence complex, while the two-electron reduction of 2 2+ causes a hapticity change from 6 to 4 on one of the naphthalene rings and yields cis-{( 5-C 5H 3) 2(CMe 2) 2}Ru 2(- 6, 4-C 10H 8) (2 0), a zwitterionic complex. The DFT calculations predict that the C s isomer of 2 0 is 4.69 kcal/mol lower in energy than the C 2v isomer, which is a transition state. Reaction of cis-{( 5-C 5H 3) 2(CMe 2) 2}Ru 2(CO) 4Br 2 with anthracene affords the analogous syn-facial anthracene complex, [cis-{( 5-C 5H 3) 2(CMe 2) 2}Ru 2(- 6, 6-C 14H 10)][OTf] 2, (4), and the tetranuclear dianthracene complex, [cis-{( 5-C 5H 3) 2(CMe 2) 2}Ru 2(- 6, 6-C 14H 10)] 2[OTf] 4, (5). 2 2+, 2 0, and 5 were structurally characterized by X-ray diffraction. 2012 American Chemical Society.
Salembier, H., Mauldin, J., Hammond, T., Wallace, R., Alqassab, E., Hall, M. B., ... Chin, R. M.
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Salembier, Helori||Mauldin, Joshua||Hammond, Tom||Wallace, Rodney||Alqassab, Essa||Hall, Michael B||Perez, Lisa M||Chen, Yuen-Jing Alexis||Turner, Katherine E||Bockoven, Eric||Brennessel, William||Chin, Robert M