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Mechanism of Formation of Copper(II) Chloro ComplexesRevealed by Transient Absorption Spectroscopy and DFT/TDDFT Calculations.

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Title: Mechanism of Formation of Copper(II) Chloro ComplexesRevealed by Transient Absorption Spectroscopy and DFT/TDDFT Calculations.
Authors: Mereshchenko, Andrey S.1, Olshin, Pavel K.1, Karabaeva, Kanykey E.1, Panov, Maxim S.1, Wilson, R. Marshall1, Kochemirovsky, Vladimir A.1, Skripkin, Mikhail Yu.1, Tveryanovich, Yury S.1, Tarnovsky, Alexander N.1
Source: Journal of Physical Chemistry B. Jul2015, Vol. 119 Issue 28, p8754-8763. 10p.
Subjects: Copper isotopes, Copper chlorides, Metal complexes, Density functional theory, Metal formability, Dissociation (Chemistry), Solvents
Abstract: Copper(II)complexes are extremely labile with typical ligand exchangerate constants on the order of 106–109M–1s–1. As a result, it isoften difficult to identify the actual formation mechanism of thesecomplexes. In this work, using UV–vis transient absorptionwhen probing in a broad time range (20 ps to 8 μs) in conjunctionwith DFT/TDDFT calculations, we studied the dynamics and underlyingreaction mechanisms of the formation of extremely labile copper(II)CuCl42–chloro complexes from copper(II)CuCl3–trichloro complexes and chlorideions. These two species, produced via photochemical dissociation ofCuCl42–upon 420 nm excitation into theligand-to-metal-charge-transfer electronic state, are found to recombineinto parent complexes with bimolecular rate constants of (9.0 ±0.1) × 107and (5.3 ± 0.4) × 108M–1s–1in acetonitrile anddichloromethane, respectively. In dichloromethane, recombination occursvia a simple one-step addition. In acetonitrile, where [CuCl3]−reacts with the solvent to form a [CuCl3CH3CN]−complex in less than20 ps, recombination takes place via ligand exchange described bythe associative interchange mechanism that involves a [CuCl4CH3CN]2–intermediate. In both solvents,the recombination reaction is potential energy controlled. [ABSTRACT FROM AUTHOR]
Copyright of Journal of Physical Chemistry B is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Mechanism of Formation of Copper(II) Chloro ComplexesRevealed by Transient Absorption Spectroscopy and DFT/TDDFT Calculations.
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Chemistry+B%22">Journal of Physical Chemistry B</searchLink>. Jul2015, Vol. 119 Issue 28, p8754-8763. 10p.
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  Data: <searchLink fieldCode="DE" term="%22Copper+isotopes%22">Copper isotopes</searchLink><br /><searchLink fieldCode="DE" term="%22Copper+chlorides%22">Copper chlorides</searchLink><br /><searchLink fieldCode="DE" term="%22Metal+complexes%22">Metal complexes</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functional+theory%22">Density functional theory</searchLink><br /><searchLink fieldCode="DE" term="%22Metal+formability%22">Metal formability</searchLink><br /><searchLink fieldCode="DE" term="%22Dissociation+%28Chemistry%29%22">Dissociation (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Solvents%22">Solvents</searchLink>
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  Data: Copper(II)complexes are extremely labile with typical ligand exchangerate constants on the order of 106–109M–1s–1. As a result, it isoften difficult to identify the actual formation mechanism of thesecomplexes. In this work, using UV–vis transient absorptionwhen probing in a broad time range (20 ps to 8 μs) in conjunctionwith DFT/TDDFT calculations, we studied the dynamics and underlyingreaction mechanisms of the formation of extremely labile copper(II)CuCl42–chloro complexes from copper(II)CuCl3–trichloro complexes and chlorideions. These two species, produced via photochemical dissociation ofCuCl42–upon 420 nm excitation into theligand-to-metal-charge-transfer electronic state, are found to recombineinto parent complexes with bimolecular rate constants of (9.0 ±0.1) × 107and (5.3 ± 0.4) × 108M–1s–1in acetonitrile anddichloromethane, respectively. In dichloromethane, recombination occursvia a simple one-step addition. In acetonitrile, where [CuCl3]−reacts with the solvent to form a [CuCl3CH3CN]−complex in less than20 ps, recombination takes place via ligand exchange described bythe associative interchange mechanism that involves a [CuCl4CH3CN]2–intermediate. In both solvents,the recombination reaction is potential energy controlled. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
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  Data: <i>Copyright of Journal of Physical Chemistry B is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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      – Type: doi
        Value: 10.1021/acs.jpcb.5b03889
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      – Code: eng
        Text: English
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        PageCount: 10
        StartPage: 8754
    Subjects:
      – SubjectFull: Copper isotopes
        Type: general
      – SubjectFull: Copper chlorides
        Type: general
      – SubjectFull: Metal complexes
        Type: general
      – SubjectFull: Density functional theory
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      – SubjectFull: Metal formability
        Type: general
      – SubjectFull: Dissociation (Chemistry)
        Type: general
      – SubjectFull: Solvents
        Type: general
    Titles:
      – TitleFull: Mechanism of Formation of Copper(II) Chloro ComplexesRevealed by Transient Absorption Spectroscopy and DFT/TDDFT Calculations.
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              Text: Jul2015
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