ABSTRACT
The possibility of existence of exohedral organometallic complexes of fullerenes larger than C60 in which their coordination can have η6 hapticity was studied from a theoretical point of view. Complexes containing C70, C74 or C60 cages, as well as cyclopentadienyl (Cp), pentamethyl-cyclopentadienyl (Me5Cp), benzene rings and hexamethyl-phenyl (Me6Ph) fragments as ligands, were designed and studied. The results show that many of these molecules can be thermodynamically stable and can have electronic interesting behavior.
ABSTRACT
Novel organometallic complexes of fullerene C80 and aryl ligands were simulated. The nature and characteristics of this family of complexes involving π coordination between the fullerene and a metal centre have been studied from a theoretical point of view. We are particularly interested in complexes where η6 coordination is present, this being the strangest manifestation of known coordinations, and thus we have studied several known and simulated compounds of this kind in order to understand the lack of examples. The presence of other η6 or η5 ligands on the opposite side seems to be an important element aiding the stabilization of these complexes, also inducing the conductive and semiconductive behaviour of the studied species.
Subject(s)
Fullerenes/chemistry , Metals/chemistry , Organometallic Compounds/chemistry , Models, MolecularABSTRACT
This study analyzes the aromatic nature of cyanuric acid (hexahydrotriazine) and some of its derivatives, in terms of aromatic stabilization energy (ASE) and electronic behavior. The simplest molecule (C(3)N(3)O(3)H(3)) is the most aromatic item out of the entire set, but some of the others also display aromatic character. The structure of all the rings is analyzed considering their molecular orbitals as well as studying the inductive effect.
Subject(s)
Hydrocarbons, Aromatic/chemistry , Triazines/chemistry , Benzyl Alcohols/chemistry , Electrochemistry , Ketones/chemistry , Models, Molecular , Molecular Conformation , Phloroglucinol/chemistryABSTRACT
The theoretical study of the interaction between CH(2) and fullerene (C(60)) suggests the existence of an addition reaction mechanism; this feature is studied by applying an analysis of electronic properties. Several different effects are evident in this interaction as a consequence of the particular electronic transfer which occurs during the procedure. The addition or insertion of the methylene group results in a process, where the inclusion of CH(2) into a fullerene bond produces the formation of several geometric deformations. A simulation of these procedures was carried out, taking advantage of the dynamic semi-classical Born-Oppenheimer approximation. Dynamic aspects were analyzed at different speeds, for the interaction between the CH(2) group and the two bonds: CC (6, 6) and CC (6, 5) respectively on the fullerene (C(60)) rings. All calculations which involved electrons employed DFT as well as exchange and functional correlation. The results indicate a tendency for the CH(2) fragment to attack the CC (6, 5) bond.
