Publication Date:
2012-05-08
Description:
The density functional theory method was used to perform quantum-chemical modeling of the mechanisms of η 2 ,η 2 -intraring (Intra-HR) and η 2 ,η 2 -interring (Inter-HR) haptotropic rearrangements for μ 2 complexes of naphthalene with rhodium, ruthenium, and osmium. The structure of transition states and intermediates was studied, and the energy parameters of haptotropic rearrangements in these complexes were determined. We used the PBE functional, the TZV2p three-exponential basis set for valence electrons, and the SBK-JC relativistic pseudopotential for core electrons. η 2 ,η 2 Intra-HR was found to occur inside the aromatic ring of η 2 naphthalene complexes without going outside it through intermediates and transition states with η n structures ( n = 1, 2). Inter-HR occurred as metal replacements on the periphery of the naphthalene ligand through intermediates and transition states with η n structures ( n = 1, 2, 3) from one ring into another. The calculated activation barriers for η 2 ,μ 2 Intra-HR and η 2 ,η 2 Inter-HR in the complexes studied closely agree with their experimental values. Content Type Journal Article Category Structure of Matter and Quantum Chemistry Pages 979-986 DOI 10.1134/S0036024412060209 Authors Yu. F. Oprunenko, Department of Chemistry, Moscow State University, Moscow, Russia I. P. Gloriozov, Department of Chemistry, Moscow State University, Moscow, Russia Journal Russian Journal of Physical Chemistry A, Focus on Chemistry Online ISSN 1531-863X Print ISSN 0036-0244 Journal Volume Volume 86 Journal Issue Volume 86, Number 6
Print ISSN:
0036-0244
Electronic ISSN:
1531-863X
Topics:
Chemistry and Pharmacology
,
Physics
