جهت دسترسی به کاربرگه ی زیر، از این لینک استفاده کنید. http://dl.pgu.ac.ir/handle/10722/70112
Title: A DFT study on the mechanism of Rh2 II, II-catalyzed intramolecular amidation of carbamates
Keywords: Rhodium;Nitrene insertion;Density functional calculations;Amidation;Reaction mechanisms;Carbamates - chemistry;Organometallic Compounds - chemistry;Thermodynamics;Amides - chemistry;Catalysis
Publisher: Wiley - V C H Verlag GmbH & Co. KGaA. The Journal's web site is located at http://www.wiley-vch.de/publish/en/journals/alphabeticIndex/2451;Germany
Description: The potential-energy surfaces of the reactions of dirhodium tetracarboxylate (Rh2 II,II) catalyzed nitrene (NR) insertion into C-H bonds were examined by a DFT computational study. A pure Becke exchange functional (B88) rather than a hybrid exchange functional (B3, BHandH) was found to be appropriate for the calculation of the energy difference between the singlet and triplet Rh2 II,II-NH nitrene species. Rh2 II,II-NR1 (R1 = (S)-2-methyl-1-butylformyl) is thermodynamically more favorable with a free energy lower than that of Rh2 II, II-N-(PhI)R1. The singlet and triplet states of Rh 2 II,II-NR1 have similar stability. Singlet Rh2 II,II-NR1 undergoes a concerted NR insertion into the C-H bond with simultaneous formation of the N-H and N-C bonds during C-H bond cleavage; triplet Rh2 II,II-NR1 undergoes H atom abstraction to produce a diradical, followed by subsequent bond formation by diradical recombination. The singlet pathway is favored over the triplet in the context of the free energy of activation and leads to the retention of the chirality of the C atom in the NR insertion product. The reactivities of the C-H bonds toward the nitrene-insertion reaction follow the order tertiary > secondary > primary. Relative reaction rates were calculated for the six reaction pathways examined in this work. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.;link_to_subscribed_fulltext
Other Identifiers: Chemistry - An Asian Journal, 2007, v. 2 n. 9, p. 1101-1108
10.1002/asia.200700068
1108
137278
WOS:000249294600004
1861-4728
9
http://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1861-4728&volume=2&issue=9&spage=1101&epage=1108&date=2007&atitle=A+DFT+study+on+the+mechanism+of+Rh2(II,II)-catalyzed+intramolecular+amidation+of+carbamates
17712831
eid_2-s2.0-34548585780
1101
http://hdl.handle.net/10722/70112
2
Type Of Material: Article
Appears in Collections:Department of Chemistry

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