The Trinuclear Copper(I) Thiolate Complexes[Cu3(NGuaS)3]0/1+ and their Dimeric Variants [Cu6(NGuaS)6]1+/2+/3+ with Biomimetic Redox Properties

Neuba, Adam; Flörke, Ülrich; Meyer‐Klaucke, Wolfram; Salomone‐Stagni, Marco; Bill, E.; Bothe, Eberhard; Höfer, Petra; Henkel, Gerald

doi:10.1002/anie.201008076

Cited by 32 publications

(35 citation statements)

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“…The species with an uneven electron number (3+ and 1+) are treated as S = 1/2 open shell systems resulting in states with an <S 2 > = 0.75 expectation value. This means that there is a single unpaired electron, in accordance with the measured EPR activity, which is discussed later …”

Section: Resultssupporting

confidence: 78%

“…It is known that nitrogen bases, guanidine ligands in special, serve as good donors in metal bonding . Hence, the ligand has been used to synthesize further polynuclear complexes, especially the complex cation [Cu 6 (NGuaS) 6 ] 2+ which is redox‐active and enables the overall charges n = 1+/2+/3+ . In this work, we utilize density functional theory (DFT) to study the bonding mechanism within the complex cations and its optical properties.…”

Section: Introductionmentioning

confidence: 99%

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[Cu₆(NGuaS)₆]²⁺ and its oxidized and reduced derivatives: Confining electrons on a torus

et al. 2017

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The hexanuclear thioguanidine mixed-valent copper complex cation [Cu (NGuaS) ] (NGuaS = o-SC H NC(NMe ) ) and its oxidized/reduced states are theoretically analyzed by means of density functional theory (DFT) (TPSSh + D3BJ/def2-TZV (p)). A detailed bonding analysis using overlap populations is performed. We find that a delocalized Cu-based ring orbital serves as an acceptor for donated S p electrons. The formed fully delocalized orbitals give rise to a confined electron cloud within the Cu S cage which becomes larger on reduction. The resulting strong electrostatic repulsion might prevent the fully reduced state. Experimental UV/Vis spectra are explained using time-dependent density functional theory (TD-DFT) and analyzed with a natural transition orbital analysis. The spectra are dominated by MLCTs within the Cu S core over a wide range but LMCTs are also found. The experimental redshift of the reduced low energy absorption band can be explained by the clustering of the frontier orbitals. © 2017 Wiley Periodicals, Inc.

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Section: Resultssupporting

confidence: 78%

Section: Introductionmentioning

confidence: 99%

[Cu₆(NGuaS)₆]²⁺ and its oxidized and reduced derivatives: Confining electrons on a torus

et al. 2017

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“…These models include the mixed‐valent complex [Cu 2 ( i PrdacoS) 2 ] + ( i PrdacoS = macrocyclic ligand with an attached thiolate moiety) of Tolman and co‐workers, which shows the characteristic seven‐line pattern of Cu A in its EPR spectrum but deviates in the Cu–Cu distance (2.93 Å) and in the nonreversible redox process . Henkel et al synthesised the hexanuclear [Cu 6 (NGuaS) 6 ] 1+/2+/3+ cation [NGuaS = o ‐SC 6 H 4 N=C(NMe 2 ) 2 ], which can reach three oxidation states through a reversible redox process . It features a short Cu–Cu distance (2.6 Å) but not the specific EPR pattern of Cu A , .…”

Section: Introductionmentioning

confidence: 99%

“…Henkel et al synthesised the hexanuclear [Cu 6 (NGuaS) 6 ] 1+/2+/3+ cation [NGuaS = o ‐SC 6 H 4 N=C(NMe 2 ) 2 ], which can reach three oxidation states through a reversible redox process . It features a short Cu–Cu distance (2.6 Å) but not the specific EPR pattern of Cu A , . The best model complex to date was characterised by Duboc et al in both biologically relevant oxidation states.…”

Section: Introductionmentioning

confidence: 99%

Copper(I) Thiolate Heteroadamantane Cage Structures with Relevance to Metalloproteins

Oppermann

Dick²,

Wehrhahn³

et al. 2016

Eur J Inorg Chem

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Cu–S heteroadamantanes are of great interest owing to their relevance to bioproteins. New copper(I) thiolate compounds with additional N‐donor functions from phenanthroline ligands have been synthesised. These complexes feature heteroadamantane cage structures with minor deviations in their construction and, therefore, a strong structural relationship. Furthermore, a decanuclear copper–sulfur cluster complex was isolated and shows known structural motifs arranged in a new fashion. Metallothioneins are natural counterparts to these complexes due to their thiolate‐rich and polynuclear d10 character. In addition to the structural characterisation, theoretical studies with a triple‐zeta basis set have been performed to further understand the building patterns of the reported complexes and their relevance to copper‐rich metalloproteins. This includes a Wiberg bond analysis and a full orbital analysis of selected heteroadamantanes to highlight the bonding interactions that connect the copper–sulfur skeletons.

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“…[27] It has been shown that type-1 centers can be structurally converted into purple Cu A centers. [29][30][31][32][33][34][35][36][37][38][39][40] The first, though not reversibly reducible, mixed-valent complex has been developed by Tolman and coworkers [41] and theoretically characterized by Solomon et al [42] Duboc and coworkers succeeded in synthesizing a mixed-valent thiolate bridged complex, showing biomimetic functionality. [29][30][31][32][33][34][35][36][37][38][39][40] The first, though not reversibly reducible, mixed-valent complex has been developed by Tolman and coworkers [41] and theoretically characterized by Solomon et al [42] Duboc and coworkers succeeded in synthesizing a mixed-valent thiolate bridged complex, showing biomimetic functionality.…”

Section: Introductionmentioning

confidence: 99%

Density functional theory of the Cu_A‐like Cu₂S₂ diamond core in Cu (NGuaS)₂Cl₂

et al. 2016

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Density functional theory (DFT) calculations with localized as well as plane-wave basis functions are performed for the recently reported dicopper thiolate species Cu2 (NGuaS)2 Cl2 [NGuaS = 2-(1,1,3,3-tetramethylguanidino) benzenethiolate, C11 H16 N3 S] and its bromo derivative [Neuba et al., Angew. Chem. Int. Ed. 2012, 51, 1714.]. For both hybrid and semilocal functionals, the neutral complexes are found to have broken symmetry (BS) character, with electron paramagnetic resonance silent, antiferromagnetically coupled [Cu(2+) …Cu(2+) ] site in which the coupling is driven by super exchange interaction within the Cu2 S2 diamond core. The accurate theoretical description of the geometric structure, however, provides a major challenge for DFT: (i) the multideterminant character of the ground state wave function has to be covered by the BS approach. It requires (ii) metageneralized gradient approximations, that is hybrid functionals with an explicit dependence on the kinetic energy of the individual orbitals: In combination with a dispersion correction, the metafunctional TPSSh results in a CuCu distance close to the experimentally observed value of 2.7 Å. For the negative charge state of the complex, a mixed-valent [Cu(1.5+) …Cu(1.5+) ] electronic structure with a smaller CuCu distance of 2.6 Å is predicted, similar to the value of the CuA site of cytochrome c oxidase.

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The Trinuclear Copper(I) Thiolate Complexes[Cu₃(NGuaS)₃]^0/1+ and their Dimeric Variants [Cu₆(NGuaS)₆]^1+/2+/3+ with Biomimetic Redox Properties

Cited by 32 publications

References 52 publications

[Cu₆(NGuaS)₆]²⁺ and its oxidized and reduced derivatives: Confining electrons on a torus

[Cu₆(NGuaS)₆]²⁺ and its oxidized and reduced derivatives: Confining electrons on a torus

Copper(I) Thiolate Heteroadamantane Cage Structures with Relevance to Metalloproteins

Density functional theory of the Cu_A‐like Cu₂S₂ diamond core in Cu (NGuaS)₂Cl₂

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The Trinuclear Copper(I) Thiolate Complexes[Cu3(NGuaS)3]0/1+ and their Dimeric Variants [Cu6(NGuaS)6]1+/2+/3+ with Biomimetic Redox Properties

Cited by 32 publications

References 52 publications

[Cu6(NGuaS)6]2+ and its oxidized and reduced derivatives: Confining electrons on a torus

[Cu6(NGuaS)6]2+ and its oxidized and reduced derivatives: Confining electrons on a torus

Copper(I) Thiolate Heteroadamantane Cage Structures with Relevance to Metalloproteins

Density functional theory of the CuA‐like Cu2S2 diamond core in Cu (NGuaS)2Cl2

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The Trinuclear Copper(I) Thiolate Complexes[Cu₃(NGuaS)₃]^0/1+ and their Dimeric Variants [Cu₆(NGuaS)₆]^1+/2+/3+ with Biomimetic Redox Properties

[Cu₆(NGuaS)₆]²⁺ and its oxidized and reduced derivatives: Confining electrons on a torus

[Cu₆(NGuaS)₆]²⁺ and its oxidized and reduced derivatives: Confining electrons on a torus

Density functional theory of the Cu_A‐like Cu₂S₂ diamond core in Cu (NGuaS)₂Cl₂