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The effects of the electronic structure and chirality of ruthenium and osmium atoms on the catalytic performance in the reduction of nitrocyclobutenes to cyclic amines are theoretically investigated using density functional theory (DFT) calculations and experimentally assessed using a model reaction with the chiral catalyst ((Mes)RuCl(2))(2), (Mes = 2,4,6-Me(3)C(6)H(2), R = H (H(2)Ru) or Ph (H(3)Ru)). The results of the DFT calculations are in good agreement with the experimental observations, confirming that the (Mes)Ru-based catalyst selectively reduces the nitro group of the substrate. The calculations indicate that, compared to the (Mes)Os-based catalyst, which has a higher initial binding energy of nitrocyclobutene, the (Mes)Ru-based catalyst exhibits a higher specificity for the substrate. The chirality of the (Mes)Ru(eta(2)-CH(2)SiR)(2) (R = H or Ph) does not affect the catalytic efficiency. However, the (Mes)Ru-based catalyst may select the preferred conformation at the initial stages of the reaction. These results indicate that the current catalyst is a promising selective catalyst for the catalytic asymmetric reduction of nitrocyclobutene-containing substrates.Daryl Mackay is reportedly retiring from the UFC, saying he’d like to retire as a champion. (AP Photo) Daryl Mackay is reportedly retiring from the UFC, saying he’d like to retire as a champion. (AP Photo)

MMA promoter Greg Jackson has long been an advocate of a partnership between mixed martial arts and the UFC. But a few weeks ago, the relationship between the UFC and the Japan-based Shooto organization started to get a little cold.

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