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http://hdl.handle.net/11701/1976
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Поле DC | Значение | Язык |
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dc.contributor.author | Mereshchenko, Andrey S | - |
dc.contributor.author | Olshin, Pavel K | - |
dc.contributor.author | Karabaeva, Kanykey E | - |
dc.contributor.author | Panov, Maxim S | - |
dc.contributor.author | Wilson, R Marshall | - |
dc.contributor.author | Kochemirovsky, Vladimir A | - |
dc.contributor.author | Skripkin, Mikhail Yu | - |
dc.contributor.author | Tveryanovich, Yury S | - |
dc.contributor.author | Tarnovsky, Alexander N | - |
dc.date.accessioned | 2016-04-08T08:40:13Z | - |
dc.date.available | 2016-04-08T08:40:13Z | - |
dc.date.issued | 2015-07-16 | - |
dc.identifier | 10.1021/acs.jpcb.5b03889 | - |
dc.identifier.issn | 10.1021/acs.jpcb.5b03889 | - |
dc.identifier.uri | http://hdl.handle.net/11701/1976 | - |
dc.description.abstract | Copper(II) complexes are extremely labile with typical ligand exchange rate constants on the order of 10(6)-10(9) M(-1) s(-1). As a result, it is often difficult to identify the actual formation mechanism of these complexes. In this work, using UV-vis transient absorption when probing in a broad time range (20 ps to 8 μs) in conjunction with DFT/TDDFT calculations, we studied the dynamics and underlying reaction mechanisms of the formation of extremely labile copper(II) CuCl4(2-) chloro complexes from copper(II) CuCl3(-) trichloro complexes and chloride ions. These two species, produced via photochemical dissociation of CuCl4(2-) upon 420 nm excitation into the ligand-to-metal-charge-transfer electronic state, are found to recombine into parent complexes with bimolecular rate constants of (9.0 ± 0.1) × 10(7) and (5.3 ± 0.4) × 10(8) M(-1) s(-1) in acetonitrile and dichloromethane, respectively. In dichloromethane, recombination occurs via a simple one-step addition. In acetonitrile, where [CuCl3](-) reacts with the solvent to form a [CuCl3CH3CN](-) complex in less than 20 ps, recombination takes place via ligand exchange described by the associative interchange mechanism that involves a [CuCl4CH3CN](2-) intermediate. In both solvents, the recombination reaction is potential energy controlled. | en_GB |
dc.language.iso | en | en_GB |
dc.title | Mechanism of Formation of Copper(II) Chloro Complexes Revealed by Transient Absorption Spectroscopy and DFT/TDDFT Calculations | en_GB |
Располагается в коллекциях: | Articles |
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Файл | Описание | Размер | Формат | |
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JPCB2015_Mechanism of Formation of Copper(II) Chloro Complexes Revealed.pdf | 1,53 MB | Adobe PDF | Просмотреть/Открыть |
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