91127-98-9Relevant academic research and scientific papers
Formation of η3-cyclooctenyl complexes from hydride transfer reactions in hydrido(cycloocta-1,5-diene)tris(ligand)ruthenium(II) cations: The dominant role of steric effects
Ashworth, Terence V.,Chalmers, Anthony A.,Meintjies, Elsie,Oosthuizen, Hester E.,Singleton, Eric
, p. 1485 - 1491 (2008/10/08)
The hydrido diene complexes [RuH(cod)L3][PF6] [1, cod = cycloocta-1,5-diene, L = P (OMe)2Ph, PMe3, PMe2Ph, P(OMe)Ph2, and PMePh2, and L3 = CH3C(CH2PPh2)3] convert irreversibly in dichloromethane or nitromethane solution to the η3-cyclooctenyl complexes [Ru(η3-C8H13)L3] [PF6], 2, in the temperature range 273-363 K. The ease of conversion of 1 to 2 may be correlated with increasing size of L. NMR studies of 2 show a bonding interaction between the metal and an endo C-H bond adjacent to the η3-allylic group. Two fluxional processes govern the appearance of the NMR spectra of 2: one process involves the mutual exchange of the three phosphorus donor ligands, whereas the other process involves the endo hydrogen atoms on the two carbon atoms adjacent to the allylic functionality. Other hydrido diene complexes [1, L = P(OMe)3, AsMe3, AsMe2Ph, and AsMePh2] do not isomerize to 2 in detectable amounts (by 1NMR) up to temperatures at which decomposition occurs. All the new compounds were isolated as analytically pure solids and were characterized by IR and 1H, 13C{1H}, and 31P{1H} NMR spectroscopy.
