title: Mechanism of Formation of Copper(II) Chloro Complexes Revealed by Transient Absorption Spectroscopy and DFT/TDDFT Calculations
metadata.name: dc.contributor.author
metadata.value: Mereshchenko, Andrey S
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Olshin, Pavel K
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Karabaeva, Kanykey E
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Panov, Maxim S
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Wilson, R Marshall
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Kochemirovsky, Vladimir A
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Skripkin, Mikhail Yu
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Tveryanovich, Yury S
metadata.lang: -
metadata.name: dc.contributor.author
metadata.value: Tarnovsky, Alexander N
metadata.lang: -
metadata.name: dc.date.accessioned
metadata.value: 2016-04-08T08:40:13Z
metadata.lang: -
metadata.name: dc.date.available
metadata.value: 2016-04-08T08:40:13Z
metadata.lang: -
metadata.name: dc.date.issued
metadata.value: 2015-07-16
metadata.lang: -
metadata.name: dc.identifier
metadata.value: 10.1021/acs.jpcb.5b03889
metadata.lang: -
metadata.name: dc.identifier.issn
metadata.value: 10.1021/acs.jpcb.5b03889
metadata.lang: -
metadata.name: dc.identifier.uri
metadata.value: http://hdl.handle.net/11701/1976
metadata.lang: -
metadata.name: dc.description.abstract
metadata.value: 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.
metadata.lang: en_GB
metadata.name: dc.language.iso
metadata.value: en
metadata.lang: en_GB
metadata.name: dc.title
metadata.value: Mechanism of Formation of Copper(II) Chloro Complexes Revealed by Transient Absorption Spectroscopy and DFT/TDDFT Calculations
metadata.lang: en_GB
resources.filename: JPCB2015_Mechanism of Formation of Copper(II) Chloro Complexes Revealed.pdf
resources.url: https://dspace.spbu.ru/bitstream/11701/1976/1/JPCB2015_Mechanism%20of%20Formation%20of%20Copper%28II%29%20Chloro%20Complexes%20Revealed.pdf
resources.format: Adobe PDF
resources.size: 1,53 MB