172371-57-2Relevant academic research and scientific papers
Cyclotriveratrylene models for proteins: 3:1 subsite differentiation and modulation of the redox potential
Strijdonck, Gino P. F. van,Haare, John A. E. H. van,Hoenen, Paulus J.M.,Schoor, Roger C. G. M. van den,Feiters, Martinus C.,et al.
, p. 449 - 462 (2007/10/03)
The potential of cyclotriveratrylene (ctv) (2,3,7,8,12,13-hexamethoxy-10,15-dihydro-5H-tribenzocyclo-nonene) trithiols as ligands that can easily be functionalised and show subsite differentiation in their complexes with clusters has been explored.The cluster complexes of tris(2-sulfanylethoxy)- and tris(3-sulfanyl-methylbenzyloxy)-functionalised ctvs have been studied by core-extrusion experiments, spectroscopy and electrochemical techniques.With 2- as starting material a cluster complex was obtained in which the unique Fe and its co-ordinating Cl was turned into the cavity and show no reactivity.Starting with the more bulky t)4>2- the unique iron points outwards and is susceptible to substitution reactions.The effects of hydrogen bonding and electron density on the redox potential of the cluster complex have been investigated.The redox potential becomes more negative when the length of the spacer between the ctv and cluster core is increased, which is explained by the longer distance between the cluster and the electron-withdrawing phenoxy moiety of the ctv.The synthesis of ctv derivatives with one thiol and one alcohol functionality per phenyl unit, and comparison with corresponding derivatives where hydrogen bonding is not possible, showed that no significant differences were found.The effects of a substituent in an aromatic amide group that could hydrogen bond to the co-ordinated thiol were investigated.A weak effect, in the direction expected, was found upon substitution of methyl for H.
Rhodium(I)-centered cyclotriveratrylene
Coolen, H. K. A. C.,Reek, J. N. H.,Ernsting, J. M.,Leeuwen, P. W. N. M. van,Nolte, R. J. M.
, p. 381 - 386 (2007/10/03)
The rigid bowl-shaped molecule cyclotriveratrylene (CTV,1) was provided with short and long spacer arms terminating in triphenyl phosphite functions.These CTV ligands were used to immobilize a rhodium(I)-carbonyl-hydride complex.The ligand with short spacers gave a rigid, strained complex with a trigonal-coordination sphere around the rhodium.The ligand with long flexible spacers allowed the formation of a large cavity after the complexation to the rhodium center.This cavity, however, is filled up by the spacer arms, as was indicated by NMR studies.Variable-temperature NMR experiments suggested that the H-Rh-CO dipole in the rhodium-CTV complex can adopt two orientations: one with the hydride group pointing away from the CTV cavity (low-temperature conformation) and one in which this orientation is inverted (high-temperature conformation).
