Diruthenium Naphthalene and Anthracene Complexes Containing a Doubly Linked Dicyclopentadienyl Ligand Academic Article uri icon

abstract

  • The reaction of cis-{(η 5-C 5H 3) 2(CMe 2) 2}Ru 2(CO) 4Br 2 with naphthalene affords the syn-facial [cis-{(η 5- C 5H 3) 2(CMe 2) 2}Ru 2(μ-η 6,η 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 π 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 η 6 to η 4 on one of the naphthalene rings and yields cis-{(η 5-C 5H 3) 2(CMe 2) 2}Ru 2(μ-η 6, η 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-{(η 5-C 5H 3) 2(CMe 2) 2}Ru 2(CO) 4Br 2 with anthracene affords the analogous syn-facial anthracene complex, [cis-{(η 5-C 5H 3) 2(CMe 2) 2}Ru 2(μ- η 6,η 6-C 14H 10)][OTf] 2, (4), and the tetranuclear dianthracene complex, [cis-{(η 5-C 5H 3) 2(CMe 2) 2}Ru 2(μ-η 6, η 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.

altmetric score

  • 0.25

author list (cited authors)

  • Salembier, H., Mauldin, J., Hammond, T., Wallace, R., Alqassab, E., Hall, M. B., ... Chin, R. M.

citation count

  • 8

publication date

  • June 2012