TY - JOUR
T1 - [(η5-C5Me5)Ru]+ fragments ligated to polyaromatic hydrocarbons
T2 - An experimental and computational approach to pathways for haptotropic migration
AU - Rioja, Matias
AU - Hamon, Paul
AU - Roisnel, Thierry
AU - Sinbandhit, Sourisak
AU - Fuentealba, Mauricio
AU - Letelier, Karina
AU - Saillard, Jean Yves
AU - Vega, Andrés
AU - Hamon, Jean René
N1 - Publisher Copyright:
© The Royal Society of Chemistry 2015.
PY - 2015/1/7
Y1 - 2015/1/7
N2 - Ligand exchange reactions between [Cp∗Ru(NCMe)3][PF6], where Cp∗ represents η5-C5Me5, and the polycyclic aromatic hydrocarbons (PAHs) pyrene, acenaphthylene and fluoranthene afforded the known [Cp∗Ru(η6-pyrene)][PF6] (1) and the new mixed sandwiches [Cp∗Ru(η6-acenaphthylene)][PF6] (2) and [Cp∗Ru(η6-fluoranthene)][PF6] (3), respectively, isolated in quantitative yields (94-100%). Complex 3 is formed as a mixture of two isomers: 3A as the major product where the [Cp∗Ru+] moiety is coordinated to the naphthalene fragment of fluoranthene, and 3B with the coordination of the arenophile to the peripheral benzene ring, in a 90/10 spectroscopic ratio. The composition and identity of the complexes were deduced by elemental analysis, 1H and 13C multidimensional NMR spectroscopy, and mass spectrometry. Compounds 1A, 3A and 2A have been characterized using X-ray structural investigations. That showed that the [Cp∗Ru+] unit is η6-attached to one of the two naphthalene rings in each complex. Heating 1 and 3 at 90 °C in CD3NO2 solutions or heating 3 at 120°C in the solid phase did not provide any evidence for thermally induced intramolecular inter-ring haptotropic rearrangements. These rearrangements were modelled by DFT calculations which indicated rather high activation energies.
AB - Ligand exchange reactions between [Cp∗Ru(NCMe)3][PF6], where Cp∗ represents η5-C5Me5, and the polycyclic aromatic hydrocarbons (PAHs) pyrene, acenaphthylene and fluoranthene afforded the known [Cp∗Ru(η6-pyrene)][PF6] (1) and the new mixed sandwiches [Cp∗Ru(η6-acenaphthylene)][PF6] (2) and [Cp∗Ru(η6-fluoranthene)][PF6] (3), respectively, isolated in quantitative yields (94-100%). Complex 3 is formed as a mixture of two isomers: 3A as the major product where the [Cp∗Ru+] moiety is coordinated to the naphthalene fragment of fluoranthene, and 3B with the coordination of the arenophile to the peripheral benzene ring, in a 90/10 spectroscopic ratio. The composition and identity of the complexes were deduced by elemental analysis, 1H and 13C multidimensional NMR spectroscopy, and mass spectrometry. Compounds 1A, 3A and 2A have been characterized using X-ray structural investigations. That showed that the [Cp∗Ru+] unit is η6-attached to one of the two naphthalene rings in each complex. Heating 1 and 3 at 90 °C in CD3NO2 solutions or heating 3 at 120°C in the solid phase did not provide any evidence for thermally induced intramolecular inter-ring haptotropic rearrangements. These rearrangements were modelled by DFT calculations which indicated rather high activation energies.
UR - http://www.scopus.com/inward/record.url?scp=84915822251&partnerID=8YFLogxK
U2 - 10.1039/c4dt02736a
DO - 10.1039/c4dt02736a
M3 - Article
AN - SCOPUS:84915822251
SN - 1477-9226
VL - 44
SP - 316
EP - 329
JO - Dalton Transactions
JF - Dalton Transactions
IS - 1
ER -