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Theoretical Investigation on the Nature of Intramolecular Interactions in Aminocyclopentadienyl Ruthenium Hydride Complexes

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journal contribution
posted on 31.07.2006 by Fuqiang Shi
Aminocyclopentadienyl ruthenium hydride complexes were optimized at the second-order Møller−Plesset (MP2) level of theory with 6-31G(d) and 6-311++G(d,p) basis sets to investigate the nature of intramolecular interactions. The computations show that both Ru−H···H−N dihydrogen bond interactions and Ru···H−N interactions are responsible for the stability of these complexes. The BSSE-corrected interaction energies, computed at the B3LYP and MP2 levels of theory with 6-31G(d), 6-311++G(d,p), and 6-311++G(2d,2p) basis sets, indicate that the dihydrogen bond interaction energy accounts for only 20% of the total interaction energy. Therefore, the Ru···H−N interactions play a key role in stabilizing the aminocyclopentadienyl ruthenium hydride complexes. Topological analysis of electron density at bond critical points confirms the formation of the dihydrogen bonds between oppositely charged hydrogen atoms. Analysis of charge distributions (Mulliken charges) shows there is a strong electronic attraction between Ru and the hydrogen atom.