期刊
DALTON TRANSACTIONS
卷 50, 期 8, 页码 2824-2831出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d0dt03706k
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资金
- Council of Scientific and Industrial Research (CSIR), New Delhi, India [01(2923)/18/EMR-II]
- University Grants Commission (UGC)
- Department of Science and Technology (DST), New Delhi, India
- UGC, New Delhi
- SERB, India [PDF/2016/001158]
- DST [IFA-17-CH286]
A mononuclear manganese(III)-peroxo complex was synthesized and studied for its reactivity in aldehyde deformylation reaction, showing nucleophilic character. Various kinetic and chemical parameters of the reaction were measured and determined.
A mononuclear manganese(iii)-peroxo complex [Mn-III(N3Py2)(O-2)](+) (1a) bearing a non-heme N,N '-dimethyl-N-(2-(methyl(pyridin-2-ylmethyl)amino)ethyl)-N '-(pyridin-2-ylmethyl)ethane-1,2-diamine (N3Py2) ligand was synthesized by the reaction of [Mn(N3Py2)(H2O)](ClO4)(2) (1) with hydrogen peroxide and triethylamine in CH3CN at 25 degrees C. The reactivity of 1a in aldehyde deformylation using 2-phenyl propionaldehyde (2-PPA) was studied and the reaction kinetics was monitored by UV-visible spectroscopy. A kinetic isotope effect (KIE) = 1.7 was obtained in the reaction of 1a with 2-PPA and alpha-[D-1]-PPA, suggesting nucleophilic character of 1a. The activation parameters Delta H-double dagger and Delta S-double dagger were determined using the Eyring plot while E-a was obtained from the Arrhenius equation by performing the reaction between 288 and 303 K. Hammett constants (sigma(p)) of para-substituted benzaldehydes p-X-Ph-CHO (X = Cl, F, H, and Me) were linear with a slope (rho) = 3.0. Computational study suggested that the side-on structure of 1a is more favored over the end-on structure and facilitates the reactivity of 1a.
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