Copper Model Complexes Research Articles

Copper(I) Nitrosyls from Reaction of Copper(II) Thiolates with S-Nitrosothiols: Mechanism of NO Release from RSNOs at Cu

S-nitrosothiols (RSNOs) serve as ready sources of biological nitric oxide activity, especially in conjunction with copper centers. We report a novel pathway for the generation of NO within the coordination sphere of copper model complexes from reaction of copper(II) thiolates with S-nitrosothiols. Reaction of tris(pyrazolyl)borate copper(II) thiolates (iPr2)TpCu-SR (R = C6F5 or CPh3) with (t)BuSNO leads to formation of (iPr2)TpCu(NO) and the unsymmetrical disulfide RS-S(t)Bu. Quantum mechanical investigations with B3LYP-D3/6-311G(d) suggest formation of a κ(1)-N-RSNO adduct (iPr2)TpCu(SR)(R'SNO) that precedes release of RSSR' to deliver (iPr2)TpCu(NO). This process is reversible; reaction of (iPr2)TpCu(NO) (but not (iPr2)TpCu(NCMe)) with C6F5S-SC6F5 forms (iPr2)TpCu-SC6F5. Coupled with the facile, reversible reaction between (iPr2)TpCu(NO) and C6F5SNO to give (iPr2)TpCu-SC6F5 and 2 equiv NO, we outline a new, detailed catalytic cycle for NO generation from RSNOs at Cu.

Molecular Basis of the Bohr Effect in Arthropod Hemocyanin

Flash photolysis and K-edge x-ray absorption spectroscopy (XAS) were used to investigate the functional and structural effects of pH on the oxygen affinity of three homologous arthropod hemocyanins (Hcs). Flash photolysis measurements showed that the well-characterized pH dependence of oxygen affinity (Bohr effect) is attributable to changes in the oxygen binding rate constant, k(on), rather than changes in k(off). In parallel, coordination geometry of copper in Hc was evaluated as a function of pH by XAS. It was found that the geometry of copper in the oxygenated protein is unchanged at all pH values investigated, while significant changes were observed for the deoxygenated protein as a function of pH. The interpretation of these changes was based on previously described correlations between spectral lineshape and coordination geometry obtained for model compounds of known structure (Blackburn, N. J., Strange, R. W., Reedijk, J., Volbeda, A., Farooq, A., Karlin, K. D., and Zubieta, J. (1989) Inorg. Chem., 28, 1349-1357). A pH-dependent change in the geometry of cuprous copper in the active site of deoxyHc, from pseudotetrahedral toward trigonal was assigned from the observed intensity dependence of the 1s --> 4p(z) transition in x-ray absorption near edge structure (XANES) spectra. The structural alteration correlated well with increase in oxygen affinity at alkaline pH determined in flash photolysis experiments. These results suggest that the oxygen binding rate in deoxyHc depends on the coordination geometry of Cu(I) and suggest a structural origin for the Bohr effect in arthropod Hcs.

DFT Calculations of EPR Parameters of Transition Metal Complexes: Implications for Catalysis

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DFT calculations of EPR parameters of transition metal complexes: Implications for catalysis

Transition metal and ligand hyperfine coupling constants for paramagnetic vanadium and copper model complexes have been calculated using DFT methods that are available in commercial software packages. Variations in EPR parameters with ligand identity and ligand orientation are two of the trends that have been investigated with DFT calculations. For example, the systematic variation of the vanadium hyperfine coupling constant with orientation for an imidazole ligand in a VO2+ complex has been observed experimentally and has also been reproduced by DFT calculations. Similarly, changes in the vanadium hyperfine coupling constant with ligand binding have been calculated using model complexes and DFT methods. DFT methods were also used to calculate ligand hyperfine coupling constants in transition metal systems. The variation of the proton hyperfine coupling constant with water ligand orientation was investigated for [VO(H2O)5]2+ and the results were used to interpret high resolution EPR data of VO2+-exchanged zeolites. Nitrogen hyperfine and quadrupole coupling constants for VO2+ model complexes were calculated and compared with experimental data. The computational results were used to enhance the interpretation of the EPR data for vanadium-exchanged zeolites which are promising catalytic materials. The implications of the DFT calculations of EPR parameters with respect to catalysis will be discussed.

Blue Copper Model Complexes with Distorted Tetragonal Geometry Acting as Effective Electron-Transfer Mediators in Dye-Sensitized Solar Cells

The electron self-exchange rate constants of blue copper model complexes, [(-)-sparteine-N,N'](maleonitriledithiolato-S,S')copper ([Cu(SP)(mmt)])(0/)(-), bis(2,9-dimethy-1,10-phenanthroline)copper ([Cu(dmp)(2)](2+/+)), and bis(1,10-phenanthroline)copper ([Cu(phen)(2)](2+/+)) have been determined from the rate constants of electron transfer from a homologous series of ferrocene derivatives to the copper(II) complexes in light of the Marcus theory of electron transfer. The resulting electron self-exchange rate constant increases in the order: [Cu(phen)(2)](2+/+) < [Cu(SP)(mmt)](0/)(-) < [Cu(dmp)(2)](2+/+), in agreement with the order of the smaller structural change between the copper(II) and copper(I) complexes due to the distorted tetragonal geometry. The dye-sensitized solar cells (DSSC) were constructed using the copper complexes as redox couples to compare the photoelectrochemical responses with those using the conventional I(3)(-)/I(-) couple. The light energy conversion efficiency (eta) values under illumination of simulated solar light irradiation (100 mW/cm(2)) of DSSCs using [Cu(phen)(2)](2+/+), [Cu(dmp)(2)](2+/+), and [Cu(SP)(mmt)](0/)(-) were recorded as 0.1%, 1.4%, and 1.3%, respectively. The maximum eta value (2.2%) was obtained for a DSSC using the [Cu(dmp)(2)](2+/+) redox couple under the light irradiation of 20 mW/cm(2) intensity, where a higher open-circuit voltage of the cell was attained as compared to that of the conventional I(3)(-)/I(-) couple.

Structural and Spectroscopic Characterization of First-Row Transition Metal(II) Substituted Blue Copper Model Complexes with Hydrotris(pyrazolyl)borate

[CuL(SC(6)F(5))] (1) (L = hydrotris(3,5-diisopropyl-1-pyrazolyl)borate anion) has been reported as a good model for blue copper proteins [Kitajima, N.; Fujisawa, K.; Tanaka, M.; Moro-oka, Y. J. Am. Chem. Soc. 1992, 114, 9232-9233]. To obtain more structural and spectroscopic insight, the first-row transition metal(II) substituted complexes of Cu(II) (1) to Mn(II) (2), Fe(II) (3), Co(II) (4), Ni(II) (5), and Zn(II) (6) were synthesized and their crystal structures were determined. These model complexes have a distorted tetrahedral geometry arising from the tripodal ligand L. The d value, which is defined by the distance from the N(2)S basal plane to the metal(II) ion, and the bond angles such as N-M-N and S-M-N are good indicators of these structural distortions. The obtained complexes were characterized by UV-vis absorption, EPR, NMR, far-IR, and FT-Raman spectroscopies and electrochemical and magnetic properties. In UV-vis absorption spectra, the sulfur-to-metal(II) CT bands and the d-d transition bands are observed for 1 and 3-5. For 1, the strong sulfur to Cu(II) CT band at 663 nm, which is one of the unique properties of blue copper proteins, is observed. The CT energies of the Fe(II) (3), Co(II) (4), and Ni(II) (5) complexes are shifted to higher energy (308 and 355 nm for 3, 311 and 340 nm for 4, 357 and 434 nm for 5) and are almost the same as the corresponding Co(II)- and Ni(II)-substituted blue copper proteins. In the far-IR spectra, three far-IR absorption bands for 2-6 at ca. 400, ca. 350, and ca. 310 cm(-1) are also observed similar to those for 1. Other properties are consistent with their distorted tetrahedral geometries.

Amido-bridged Cu2N2 diamond cores that minimize structural reorganization and facilitate reversible redox behavior between a Cu1Cu1 and a class III delocalized Cu1.5Cu1.5 species.

A novel Cu(2)N(2) diamond core structure supported by an [SNS](-) ligand (1) ([SNS](-) = bis(2-tert-butylsulfanylphenyl)amido) has been prepared. This dicopper system exhibits a fully reversible one-electron redox process between a reduced Cu(1)Cu(1) complex, [[SNS][Cu]](2) (2), and a class III delocalized Cu(1.5)Cu(1.5) state, [[[SNS][Cu]](2)][B(3,5-(CF(3))(2)C(6)H(3))(4)] (3). Structural snapshots of both redox forms have been obtained to reveal remarkably little overall structural reorganization. The Cu...Cu bond distance nonetheless undergoes an appreciable compression (approximately 0.13 A) upon oxidation, providing a Cu...Cu distance of 2.4724(4) A in the mixed-valence state that is virtually identical to the Cu...Cu distance observed in the reduced form of the Cu(A) site of thiolate-bridged cytochrome c oxidase. Despite the low structural reorganization evident between 2 and 3, the [SNS](-) ligand is quite flexible. For example, square-planar geometries can prevail for divalent copper ions supported by [SNS](-) as evident from the crystal structure of [SNS]CuCl (4). Physical characterization for the mixed valence complex 3 includes electrochemical, magnetic (SQUID), EPR, and optical data. The complex has also been examined by density functional methods. An attempt was made to measure the rate of electron self-exchange k(s) between the Cu(1)Cu(1) and the Cu(1.5)Cu(1.5) complexes 2 and 3 by NMR line-broadening analysis in dichloromethane solution. While the system is certainly in the fast-exchange regime, the exchange process is too fast to be accurately measured by this technique. The value for k(s) can be bracketed with a conservative lower boundary of > or =10(7) M(-1) s(-1), a value that appears to be larger than other low molecular weight copper model complexes for which similar data is available. The unusually large magnitude of k(s) likely reflects the minimal structural reorganization that accompanies Cu(1)Cu(1) <--> Cu(1.5)Cu(1.5) interchange.

Spectroscopic and Electronic Structural Studies of Blue Copper Model Complexes. 2. Comparison of Three- and Four-Coordinate Cu(II)−Thiolate Complexes and Fungal Laccase

To evaluate the importance of the axial ligand in blue Cu centers, the electronic structure of a three-coordinate model compound LCuSCPh3 (2, L = β-diketiminate ligand) is defined using low-temperature absorption, magnetic circular dichroism (MCD), X-ray absorption spectroscopy (XAS), and resonance Raman (rR) profiles coupled with density functional calculations. Using these excited-state spectroscopic methods the electronic structure of 2 is compared to that of a four-coordinate blue Cu model compound LCuSCPh3 (1, L = tris(pyrazolyl)hydroborate ligand) and the three-coordinate blue Cu center in fungal laccase. The spectral features of 2 are substantially altered from those of 1 and reflect a trans influence of the β-diketiminate ligand that involves a strong interaction with the Cu dx2-y2 orbital, concomitant with a decreased S pπ interaction with the Cu dx2-y2 orbital. The lack of an axial ligand coupled with the influence of this equatorial donor leads to many of the perturbed spectral features of 2 relative to 1 including: the shift of the S pπ → Cu CT transition to lower energy and its reduced intensity, the stronger ligand field, the larger nitrogen covalency in the HOMO at the expense of thiolate covalency, and the decreased excited-state distortion. From XAS, it also is clear that loss of the axial pyrazole ligand in 2 relative to 1 leads to an increase in the effective nuclear charge of the three-coordinate Cu in 2, which demonstrates that the axial ligand modulates the electronic structure. From a comparison of 2 to fungal laccase it is evident that even in the absence of an axial ligand the electronic structure can be modulated by differential charge donation from the equatorial ligands. These studies show that elimination of the axial ligand of the blue copper site can affect the covalency of the thiolate−Cu bond and potentially modify the electron-transfer properties of the site.

Redox behavior of blue copper model complexes. Redox potentials and electron-transfer kinetics of some copper(II)-copper(I) complexes with nitrogen and thioether donors

Determination potentiometrique des potentiels redox Cu II -Cu I et des constantes de vitesse pour la reduction a 1 electron des complexes de Cu(II) avec les thioethers. Il ne semble pas que la geometrie des coordinats tripodes augmente de facon sensible la vitesse de transfert d'electron