Thermodynamics of the CuII μ-Thiolate and CuI Disulfide Equilibrium: A Combined Experimental and Theoretical Study

Erica C. M. Ording-Wenker; Martijn van der Plas; Maxime A. Siegler; Sylvestre Bonnet; F. Matthias Bickelhaupt; Celia Fonseca Guerra; Elisabeth Bouwman

doi:10.1021/ic501060w

Thermodynamics of the Cu^II μ-Thiolate and Cu^I Disulfide Equilibrium: A Combined Experimental and Theoretical Study

Erica C. M. Ording-Wenker, Martijn van der Plas, Maxime A. Siegler, Sylvestre Bonnet, F. Matthias Bickelhaupt, Celia Fonseca Guerra, Elisabeth Bouwman

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

The redox equilibrium between dinuclear CuII
μ-thiolate and CuI disulfide structures has been analyzed
experimentally and via DFT calculations. Two new ligands,
L2SSL2 and L4SSL4, and their CuII μ-thiolate and CuI disulfide
complexes were synthesized. For L2SSL2, these two redoxisomeric
copper species are shown to be in equilibrium, which
depends on both temperature and solvent. For L4SSL4 the μ-
thiolate species forms as the kinetic product and further
evolves into the disulfide complex under thermodynamic
control, which creates the unprecedented possibility to
compare both species under the same reaction conditions.
The energies of the μ-thiolate and disulfide complexes for two
series of related ligands have been calculated with DFT; the
results rationalize the experimentally observed structures, and emphasize the important role that steric requirements play in the
formation of the CuII thiolate structure.

Original language	English
Pages (from-to)	8494-8504
Number of pages	11
Journal	Inorganic Chemistry
Volume	53
Issue number	16
DOIs	https://doi.org/10.1021/ic501060w
Publication status	Published - 4 Aug 2014

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10.1021/ic501060w

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CCDC 1030013: Experimental Crystal Structure Determination
Ording-Wenker, E. C. M. (Contributor), Van Der Plas, M. (Contributor), Siegler, M. A. (Contributor), Bonnet, S. (Contributor), Bickelhaupt, M. (Contributor), Guerra, C. F. (Contributor) & Bouwman, E. (Contributor), Unknown Publisher, 18 Aug 2014
DOI: 10.5517/cc13kt7q, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc13kt7q&sid=DataCite
Dataset / Software: Dataset
CCDC 1030012: Experimental Crystal Structure Determination
Ording-Wenker, E. C. M. (Contributor), Van Der Plas, M. (Contributor), Siegler, M. A. (Contributor), Bonnet, S. (Contributor), Bickelhaupt, M. (Contributor), Guerra, C. F. (Contributor) & Bouwman, E. (Contributor), Unknown Publisher, 18 Aug 2014
DOI: 10.5517/cc13kt6p, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc13kt6p&sid=DataCite
Dataset / Software: Dataset
CCDC 1030011: Experimental Crystal Structure Determination
Ording-Wenker, E. C. M. (Contributor), Van Der Plas, M. (Contributor), Siegler, M. A. (Contributor), Bonnet, S. (Contributor), Bickelhaupt, M. (Contributor), Guerra, C. F. (Contributor) & Bouwman, E. (Contributor), Unknown Publisher, 18 Aug 2014
DOI: 10.5517/cc13kt5n, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc13kt5n&sid=DataCite
Dataset / Software: Dataset

Cite this

@article{03a300e435084cadb8e911cdd63c009e,

title = "Thermodynamics of the CuII μ-Thiolate and CuI Disulfide Equilibrium: A Combined Experimental and Theoretical Study",

abstract = "The redox equilibrium between dinuclear CuIIμ-thiolate and CuI disulfide structures has been analyzedexperimentally and via DFT calculations. Two new ligands,L2SSL2 and L4SSL4, and their CuII μ-thiolate and CuI disulfidecomplexes were synthesized. For L2SSL2, these two redoxisomericcopper species are shown to be in equilibrium, whichdepends on both temperature and solvent. For L4SSL4 the μ-thiolate species forms as the kinetic product and furtherevolves into the disulfide complex under thermodynamiccontrol, which creates the unprecedented possibility tocompare both species under the same reaction conditions.The energies of the μ-thiolate and disulfide complexes for twoseries of related ligands have been calculated with DFT; theresults rationalize the experimentally observed structures, and emphasize the important role that steric requirements play in theformation of the CuII thiolate structure.",

author = "Ording-Wenker, {Erica C. M.} and {van der Plas}, Martijn and Siegler, {Maxime A.} and Sylvestre Bonnet and Bickelhaupt, {F. Matthias} and Guerra, {Celia Fonseca} and Elisabeth Bouwman",

year = "2014",

month = aug,

day = "4",

doi = "10.1021/ic501060w",

language = "English",

volume = "53",

pages = "8494--8504",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "16",

}

TY - JOUR

T1 - Thermodynamics of the CuII μ-Thiolate and CuI Disulfide Equilibrium

T2 - A Combined Experimental and Theoretical Study

AU - Ording-Wenker, Erica C. M.

AU - van der Plas, Martijn

AU - Siegler, Maxime A.

AU - Bonnet, Sylvestre

AU - Bickelhaupt, F. Matthias

AU - Guerra, Celia Fonseca

AU - Bouwman, Elisabeth

PY - 2014/8/4

Y1 - 2014/8/4

N2 - The redox equilibrium between dinuclear CuIIμ-thiolate and CuI disulfide structures has been analyzedexperimentally and via DFT calculations. Two new ligands,L2SSL2 and L4SSL4, and their CuII μ-thiolate and CuI disulfidecomplexes were synthesized. For L2SSL2, these two redoxisomericcopper species are shown to be in equilibrium, whichdepends on both temperature and solvent. For L4SSL4 the μ-thiolate species forms as the kinetic product and furtherevolves into the disulfide complex under thermodynamiccontrol, which creates the unprecedented possibility tocompare both species under the same reaction conditions.The energies of the μ-thiolate and disulfide complexes for twoseries of related ligands have been calculated with DFT; theresults rationalize the experimentally observed structures, and emphasize the important role that steric requirements play in theformation of the CuII thiolate structure.

AB - The redox equilibrium between dinuclear CuIIμ-thiolate and CuI disulfide structures has been analyzedexperimentally and via DFT calculations. Two new ligands,L2SSL2 and L4SSL4, and their CuII μ-thiolate and CuI disulfidecomplexes were synthesized. For L2SSL2, these two redoxisomericcopper species are shown to be in equilibrium, whichdepends on both temperature and solvent. For L4SSL4 the μ-thiolate species forms as the kinetic product and furtherevolves into the disulfide complex under thermodynamiccontrol, which creates the unprecedented possibility tocompare both species under the same reaction conditions.The energies of the μ-thiolate and disulfide complexes for twoseries of related ligands have been calculated with DFT; theresults rationalize the experimentally observed structures, and emphasize the important role that steric requirements play in theformation of the CuII thiolate structure.

U2 - 10.1021/ic501060w

DO - 10.1021/ic501060w

M3 - Article

SN - 0020-1669

VL - 53

SP - 8494

EP - 8504

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 16

ER -

Thermodynamics of the CuII μ-Thiolate and CuI Disulfide Equilibrium: A Combined Experimental and Theoretical Study

Abstract

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Datasets

CCDC 1030013: Experimental Crystal Structure Determination

CCDC 1030012: Experimental Crystal Structure Determination

CCDC 1030011: Experimental Crystal Structure Determination

Cite this

Thermodynamics of the Cu^II μ-Thiolate and Cu^I Disulfide Equilibrium: A Combined Experimental and Theoretical Study