Copper(I) Complex O(2)-Reactivity With a N(3)S Thioether Ligand: a Copper-Dioxygen Adduct Including Sulfur Ligation, Ligand Oxygenation, And Comparisons With All Nitrogen Ligand Analogues

Title: Copper(I) Complex O(2)-Reactivity With a N(3)S Thioether Ligand: a Copper-Dioxygen Adduct Including Sulfur Ligation, Ligand Oxygenation, And Comparisons With All Nitrogen Ligand Analogues

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Abstract

In order to contribute to an understanding of the effects of thioether sulfur ligation in copper-O(2) reactivity, the tetradentate ligands L(N3S) (2-ethylthio-N,N-bis(pyridin-2-yl)methylethanamine) and L(N3S')(2-ethylthio-N,N-bis(pyridin-2-yl)ethylethanamine) have been synthesized. Corresponding copper(I) complexes, [CuI(L(N3S))]ClO(4) (1-ClO(4)), [CuI(L(N3S))]B(C(6)F(5))(4) (1-B(C(6)F(5))(4)), and [CuI(L(N3S'))]ClO(4) (2), were generated, and their redox properties, CO binding, and O(2)-reactivity were compared to the situation with analogous compounds having all nitrogen donor ligands, [CuI(TMPA)(MeCN)](+) and [Cu(I)(PMAP)](+) (TMPA = tris(2-pyridylmethyl)amine; PMAP = bis[2-(2-pyridyl)ethyl]-(2-pyridyl)methylamine). X-ray structures of 1-B(C(6)F(5))(4), a dimer, and copper(II) complex [Cu(II)(L(N3S))(MeOH)](ClO(4))(2) (3) were obtained; the latter possesses axial thioether coordination. At low temperature in CH(2)Cl(2), acetone, or 2-methyltetrahydrofuran (MeTHF), 1 reacts with O(2) and generates an adduct formulated as an end-on peroxodicopper(II) complex [{l_brace}Cu(II)(L(N3S)){r_brace}(2)(mu-1,2-O(2)(2-))](2+) (4){lambda}(max) = 530 (epsilon approximately 9200 M(-1) cm(-1)) and 605 nm (epsilon approximately 11,800 M(-1) cm(-1)); the number and relative intensity of LMCT UV-vis bands vary from those for [{l_brace}Cu(II)(TMPA){r_brace}(2)(O(2)(2-))](2+) {lambda}(max) = 524 nm (epsilon = 11,300 M(-1) cm(-1)) and 615 nm (epsilon = 5800 M(-1) cm(-1)) and are ascribed to electronic structure variation due to coordination geometry changes with the L(N3S) ligand. Resonance Raman spectroscopy confirms the end-on peroxo-formulation {nu}(O-O) = 817 cm(-1) (16-18O(2) Delta = 46 cm(-1)) and nu(Cu-O) = 545 cm(-1) (16-18O(2) Delta = 26more »« less

Authors:: Lee, D -H; Hatcher, L Q; Vance, M A; Sarangi, R; Milligan, A E; Sarjeant, A A Narducci; Incarvito, C D; Rheingold, A L; Hodgson, K O; Hedman, B; Solomon, E I; Karlin, K D

Publication Date:: 2009-06-03

Research Org.:: Stanford Linear Accelerator Center (SLAC)

Sponsoring Org.:: USDOE

OSTI Identifier:: 953935

Report Number(s):: SLAC-REPRINT-2009-457
Journal ID: ISSN 0020-1669; INOCAJ; TRN: US201004%%672

DOE Contract Number:: AC02-76SF00515

Resource Type:: Journal Article

Journal Name:: Inorg. Chem. 46:6056,2007

Additional Journal Information:: Journal Volume: 46; Journal Issue: 15; Journal ID: ISSN 0020-1669

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACETONE; ADDUCTS; BIOLOGICAL STRESS; CHELATES; CHEMISTRY; COPPER COMPLEXES; COPPER; ELECTRON DENSITY; ELECTRONIC STRUCTURE; ENZYMES; LIGANDS; METHIONINE; NITROGEN; ORGANIC SULFUR COMPOUNDS; OXIDATION; PEROXIDES; RAMAN SPECTROSCOPY; REACTIVITY; REDOX POTENTIAL; RESONANCE; SIMULATION; SPECTROSCOPY; SULFOXIDES; SULFUR; TEMPERATURE RANGE 0065-0273 K; VARIATIONS; Other,OTHER, CHEM

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                    Lee, D -H, Hatcher, L Q, Vance, M A, Sarangi, R, Milligan, A E, Sarjeant, A A Narducci, Incarvito, C D, Rheingold, A L, Hodgson, K O, Hedman, B, Solomon, E I, and Karlin, K D. Copper(I) Complex O(2)-Reactivity With a N(3)S Thioether Ligand: a Copper-Dioxygen Adduct Including Sulfur Ligation, Ligand Oxygenation, And Comparisons With All Nitrogen Ligand Analogues.  United States: N. p., 2009. 
        Web.

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                    Lee, D -H, Hatcher, L Q, Vance, M A, Sarangi, R, Milligan, A E, Sarjeant, A A Narducci, Incarvito, C D, Rheingold, A L, Hodgson, K O, Hedman, B, Solomon, E I, & Karlin, K D. Copper(I) Complex O(2)-Reactivity With a N(3)S Thioether Ligand: a Copper-Dioxygen Adduct Including Sulfur Ligation, Ligand Oxygenation, And Comparisons With All Nitrogen Ligand Analogues.  United States.

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                    Lee, D -H, Hatcher, L Q, Vance, M A, Sarangi, R, Milligan, A E, Sarjeant, A A Narducci, Incarvito, C D, Rheingold, A L, Hodgson, K O, Hedman, B, Solomon, E I, and Karlin, K D. Wed .  
        "Copper(I) Complex O(2)-Reactivity With a N(3)S Thioether Ligand: a Copper-Dioxygen Adduct Including Sulfur Ligation, Ligand Oxygenation, And Comparisons With All Nitrogen Ligand Analogues".  United States.

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@article{osti_953935,

  title        = {Copper(I) Complex O(2)-Reactivity With a N(3)S Thioether Ligand: a Copper-Dioxygen Adduct Including Sulfur Ligation, Ligand Oxygenation, And Comparisons With All Nitrogen Ligand Analogues},

  author       = {Lee, D -H and Hatcher, L Q and Vance, M A and Sarangi, R and Milligan, A E and Sarjeant, A A Narducci and Incarvito, C D and Rheingold, A L and Hodgson, K O and Hedman, B and Solomon, E I and Karlin, K D},

  abstractNote = {In order to contribute to an understanding of the effects of thioether sulfur ligation in copper-O(2) reactivity, the tetradentate ligands L(N3S) (2-ethylthio-N,N-bis(pyridin-2-yl)methylethanamine) and L(N3S')(2-ethylthio-N,N-bis(pyridin-2-yl)ethylethanamine) have been synthesized. Corresponding copper(I) complexes, [CuI(L(N3S))]ClO(4) (1-ClO(4)), [CuI(L(N3S))]B(C(6)F(5))(4) (1-B(C(6)F(5))(4)), and [CuI(L(N3S'))]ClO(4) (2), were generated, and their redox properties, CO binding, and O(2)-reactivity were compared to the situation with analogous compounds having all nitrogen donor ligands, [CuI(TMPA)(MeCN)](+) and [Cu(I)(PMAP)](+) (TMPA = tris(2-pyridylmethyl)amine; PMAP = bis[2-(2-pyridyl)ethyl]-(2-pyridyl)methylamine). X-ray structures of 1-B(C(6)F(5))(4), a dimer, and copper(II) complex [Cu(II)(L(N3S))(MeOH)](ClO(4))(2) (3) were obtained; the latter possesses axial thioether coordination. At low temperature in CH(2)Cl(2), acetone, or 2-methyltetrahydrofuran (MeTHF), 1 reacts with O(2) and generates an adduct formulated as an end-on peroxodicopper(II) complex [{l_brace}Cu(II)(L(N3S)){r_brace}(2)(mu-1,2-O(2)(2-))](2+) (4){lambda}(max) = 530 (epsilon approximately 9200 M(-1) cm(-1)) and 605 nm (epsilon approximately 11,800 M(-1) cm(-1)); the number and relative intensity of LMCT UV-vis bands vary from those for [{l_brace}Cu(II)(TMPA){r_brace}(2)(O(2)(2-))](2+) {lambda}(max) = 524 nm (epsilon = 11,300 M(-1) cm(-1)) and 615 nm (epsilon = 5800 M(-1) cm(-1)) and are ascribed to electronic structure variation due to coordination geometry changes with the L(N3S) ligand. Resonance Raman spectroscopy confirms the end-on peroxo-formulation {nu}(O-O) = 817 cm(-1) (16-18O(2) Delta = 46 cm(-1)) and nu(Cu-O) = 545 cm(-1) (16-18O(2) Delta = 26 cm(-1)); these values are lower in energy than those for [{l_brace}Cu(II)(TMPA){r_brace}(2)(O(2)(2-))](2+) {nu}(Cu-O) = 561 cm(-1) and nu(O-O) = 827 cm(-1) and can be attributed to less electron density donation from the peroxide pi* orbitals to the Cu(II) ion. Complex 4 is the first copper-dioxygen adduct with thioether ligation; direct evidence comes from EXAFS spectroscopy {l_brace}Cu K-edge; Cu-S = 2.4 Angstrom{r_brace}. Following a [Cu(I)(L(N3S))](+)/O(2) reaction and warming, the L(N3S) thioether ligand is oxidized to the sulfoxide in a reaction modeling copper monooxygenase activity. By contrast, 2 is unreactive toward dioxygen probably due to its significantly increased Cu(II)/Cu(I) redox potential, an effect of ligand chelate ring size (in comparison to 1). Discussion of the relevance of the chemistry to copper enzyme O(2)-activation, and situations of biological stress involving methionine oxidation, is provided.},

  doi          = {},

  url          = {https://www.osti.gov/biblio/953935},
  journal      = {Inorg. Chem. 46:6056,2007},

  issn         = {0020-1669},

  number       = 15,

  volume       = 46,

  place        = {United States},

  year         = {2009},

  month        = {6}

}

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