Abstract

synthesized and characterized by H-1, C-13, P-31 NMR and IR spectroscopies. The reaction of MnCl2 center dot 4H(2)O with L led to the formation of a new 3D system {MnL2Cl2}(n)center dot 34CH(3)OH (C-1). X-ray crystallographic data revealed that the ligand binds to the neighboring manganese ions through the nitrogen atom of pyridine (N-py) and the oxygen atom of phosphoryl (O-P) in a bidentate manner. The Mn(II) centers showed a distorted cis(N-py, N-py) cis(O-P, O-P) cis(Cl, Cl) octahedral configuration. In order to compare the relative stability of C-1 (with all-cis configuration) and its possible all-trans isomer, C-1', density functional theory (DFT) calculations were performed and the results showed the preference of C-1 over C-1' from energy point of view. Quantum theory of atoms in molecules (QTAIM) analysis was applied to elucidate the nature of interactions, and the results suggested an ionic character (closed-shell interaction) for Mn-OP bond, and a partial covalent contribution for Mn-N-py interaction. Natural bond orbital (NBO) analysis was also used to calculate the charge distribution on atoms in the complex. The complex C-1 showed efficient catalytic activity in the oxidation reaction of some alkenes to their corresponding epoxides. In addition, the effect of temperature and reaction time on the conversion and selectivity of cyclohexene epoxidation reaction in the presence of C-1 as catalyst was investigated. (C) 2015 Elsevier B.V. All rights reserved.

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