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Title: Dioxygen Reactivity of a Copper(I) Complex With a N3S Thioether Chelate Peroxo-Dicopper(II) Formation Including Sulfur-Ligation

Abstract

No abstract prepared.

Authors:
; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Stanford Linear Accelerator Center (SLAC)
Sponsoring Org.:
USDOE
OSTI Identifier:
897747
Report Number(s):
SLAC-REPRINT-2006-188
TRN: US200705%%238
DOE Contract Number:
AC02-76SF00515
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorg.Chem.45:10055, 2006
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHELATES; ORGANIC SULFUR COMPOUNDS; COPPER COMPLEXES; ACTIVATION ENERGY; CHEMICAL REACTION KINETICS; Other,OTHER

Citation Formats

Hatcher, L.Q., Lee, D.H., Vance, M.A., Milligan, A.E., Sarangi, R., Hodgson, K.O., Hedman, B., Solomon, E.I., Karlin, K.D., and /Johns Hopkins U. /Chonbuk Natl. U. /Stanford U., Chem. Dept. /SLAC, SSRL. Dioxygen Reactivity of a Copper(I) Complex With a N3S Thioether Chelate Peroxo-Dicopper(II) Formation Including Sulfur-Ligation. United States: N. p., 2007. Web.
Hatcher, L.Q., Lee, D.H., Vance, M.A., Milligan, A.E., Sarangi, R., Hodgson, K.O., Hedman, B., Solomon, E.I., Karlin, K.D., & /Johns Hopkins U. /Chonbuk Natl. U. /Stanford U., Chem. Dept. /SLAC, SSRL. Dioxygen Reactivity of a Copper(I) Complex With a N3S Thioether Chelate Peroxo-Dicopper(II) Formation Including Sulfur-Ligation. United States.
Hatcher, L.Q., Lee, D.H., Vance, M.A., Milligan, A.E., Sarangi, R., Hodgson, K.O., Hedman, B., Solomon, E.I., Karlin, K.D., and /Johns Hopkins U. /Chonbuk Natl. U. /Stanford U., Chem. Dept. /SLAC, SSRL. Tue . "Dioxygen Reactivity of a Copper(I) Complex With a N3S Thioether Chelate Peroxo-Dicopper(II) Formation Including Sulfur-Ligation". United States. doi:.
@article{osti_897747,
title = {Dioxygen Reactivity of a Copper(I) Complex With a N3S Thioether Chelate Peroxo-Dicopper(II) Formation Including Sulfur-Ligation},
author = {Hatcher, L.Q. and Lee, D.H. and Vance, M.A. and Milligan, A.E. and Sarangi, R. and Hodgson, K.O. and Hedman, B. and Solomon, E.I. and Karlin, K.D. and /Johns Hopkins U. /Chonbuk Natl. U. /Stanford U., Chem. Dept. /SLAC, SSRL},
abstractNote = {No abstract prepared.},
doi = {},
journal = {Inorg.Chem.45:10055, 2006},
number = ,
volume = ,
place = {United States},
year = {Tue Jan 16 00:00:00 EST 2007},
month = {Tue Jan 16 00:00:00 EST 2007}
}
  • 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 withmore » 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.« less
  • Compounds of the general formula Cu/sub m/I/sub m/(PR/sub 3/)/sub n/ . xSO/sub 2/, where PR/sub 3/ = PPh/sub 3/, PPh/sub 2/Me, PBzl/sub 3/, and PCy/sub 3/ (Bzl = benzyl; Cy = cyclohexyl), are formed by direct reaction of SO/sub 2/ with organophosphine copper (I) iodide complexes. The nature of the reaction solutions and isolated products has been elucidated by spectroscopic, tensimetric, and x-ray diffraction methods. Sulfur dioxide complexation occurs only at the coordinated halogen, even when three-coordinate copper (I) apparently is present in the complex. The strength of interaction is a strong function of both the specific phosphine and stoichiometry,more » and the bright yellow to orange crystalline complexes have SO/sub 2/ dissociation pressures of 2 to 70 Torr at ambient temperature. The crystal structure analysis of Cu/sub 2/I/sub 2/(PPh/sub 2/Me)/sub 4/ . SO/sub 2/ reveals a dimeric, di-..mu..-iodo-bridged structure involving pseudotetrahedral copper atoms and an SO/sub 2/ group bound weakly as a Lewis acid to one of the bridging iodides (I--S = 3.407 (5) A and I--S--O = 98.1 (6), 114.5 (8)/sup 0/). Additionally, we report the structure of the compound Cu/sub 2/I/sub 2/(PPh/sub 3/)/sub 3/ and its interaction with sulfur dioxide. X-ray structure determination reveals a dinuclear unit similar to that found in Cu/sub 2/Cl/sub 2/(PPh/sub 3/)/sub 3/ with ..mu..-iodide bridges and both three-coordinate copper and four-coordinate copper. Pertinent crystallographic data are as follows: Cu/sub 2/I/sub 2/(PPh/sub 3/)/sub 3/, space group P2/sub 1/, a = 11.763 (4) A, b = 20.682 (4) A, c = 10.527 (3) A, ..beta.. = 105.66 (2)/sup 0/, Z = 2, R = 0.047 for 4139 diffractometric reflections (with I greater than or equal to 3sigma(I) and 2theta less than or equal to 60/sup 0/); Cu/sub 2/I/sub 2/(PPh/sub 2/Me)/sub 4/SO/sub 2/, space group P anti l, a = 20.02 (2) A, b = 12.062 (6) A, c = 14.898 (7) A, ..cap alpha.. = 116.30 (3)/sup 0/, ..beta.. = 68.44 (3)/sup 0/, ..gamma.. = 124.89 (2)/sup 0/, Z = 2, R = 0.052 for 7112 diffractometric reflections (with I greater than or equal to 3sigma(I) and 2sigma less than or equal to 50/sup 0/).« less
  • Prompted by the potential analogy of thioethers to phosphines and by the occurrence of thioether coordination in blue copper proteins, they have recently been investigating the properties of homoleptic hexakis(thioether) complexes of transition-metal ions. Earlier work has shown that this new environment can be imposed on transition-metal ions by coordination to crown thioethers and that it induces unusual electronic structure - and therefore perhaps unusual reactivity - on them. Any future applications of homoleptic thioether complexes of crown-type ligands will, however, be hindered by the somewhat involved synthesis of the ligands. They now wish to report their initial work onmore » the preparation and coordination chemistry of 1,1,1-tris(((2-(methylthio)ethyl)thio)methyl)ethane (L), a new ligand that makes the homoleptic hexakis(thioether) environment readily available. Moreover, the synthesis used here may afford a general route into analogous three dimensionally articulated ligands.« less