[Cu3(μ-S)2]3+ clusters supported by N-donor ligands:: Progress toward a synthetic model of the catalytic site of nitrous oxide reductase

被引:78
作者
Brown, EC
York, JT
Antholine, WE
Ruiz, E
Alvarez, S
Tolman, WB
机构
[1] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA
[2] Univ Minnesota, Ctr Metals Biocatalysis, Minneapolis, MN 55455 USA
[3] Med Coll Wisconsin, Dept Biophys, Milwaukee, WI 53226 USA
[4] Univ Barcelona, Dept Quim Inorgan, Barcelona 08028, Spain
关键词
D O I
10.1021/ja053971t
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
By treating Cu(I) complexes of neutral, bidentate N-donor ligands with S8, clusters with novel delocalized mixed-valence [Cu3(μ-S)2]3+ cores have been isolated. X-ray crystal structures and UV-vis and resonance Raman spectral features of these clusters reveal similarities to the tetracopper-sulfide "CuZ" site in nitrous oxide reductase. A delocalized S = 1 ground state for the mixed-valent CuIIICu2II cores is supported by the observation of high symmetry in the X-ray structures and 10-line hyperfine features arising from coupling to three equivalent Cu ions in EPR spectra obtained at room temperature (shown) and 10 K. The delocalization we observe contrasts with the localization reported previously for a [Cu3(μ-O)2]3+ analogue (Root, D. E.; Henson, M. J.; Machonkin, T.; Mukherjee, P.; Stack, T. D. P.; Solomon, E. I. J. Am. Chem. Soc. 1998, 120, 4982), which we rationalized through DFT calculations. Copyright © 2005 American Chemical Society.
引用
收藏
页码:13752 / 13753
页数:2
相关论文
共 25 条
[1]   Characterization of the copper-sulfur chromophores in nitrous oxide reductase by resonance Raman spectroscopy: Evidence for sulfur coordination in the catalytic cluster [J].
Alvarez, ML ;
Ai, JY ;
Zumft, W ;
Sanders-Loehr, J ;
Dooley, DM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (04) :576-587
[2]   Formation of sulfur-sulfur bonds in copper complexes [J].
Aullón, G ;
Alvarez, S .
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2004, (22) :4430-4438
[3]   A new class of (μ-η2:η2-disulfido)dicopper complexes:: Synthesis characterization and disulfido exchange [J].
Brown, EC ;
Aboelella, NW ;
Reynolds, AM ;
Aullón, G ;
Alvarez, S ;
Tolman, WB .
INORGANIC CHEMISTRY, 2004, 43 (11) :3335-3337
[4]   Revisiting the catalytic CuZ cluster of nitrous oxide (N2O) reductase -: Evidence of a bridging inorganic sulfur [J].
Brown, K ;
Djinovic-Carugo, K ;
Haltia, T ;
Cabrito, I ;
Saraste, M ;
Moura, JJG ;
Moura, I ;
Tegoni, M ;
Cambillau, C .
JOURNAL OF BIOLOGICAL CHEMISTRY, 2000, 275 (52) :41133-41136
[5]   Reductively activated nitrous oxide reductase reacts directly with substrate [J].
Chan, JM ;
Bollinger, JA ;
Grewell, CL ;
Dooley, DM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (10) :3030-3031
[6]   N2O reduction by the μ4-sulfide-bridged tetranuclear CuZ cluster active site [J].
Chen, P ;
Gorelsky, SI ;
Ghosh, S ;
Solomon, EI .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (32) :4132-4140
[7]   Spectroscopy and bonding in side-on and end-on Cu2(S2) cores:: Comparison to peroxide analogues [J].
Chen, P ;
Fujisawa, K ;
Helton, ME ;
Karlin, KD ;
Solomon, EI .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (21) :6394-6408
[8]   Spectroscopic and electronic structure studies of the μ4-sulfide bridged tetranuclear Cuz cluster in N2O reductase:: Molecular insight into the catalytic mechanism [J].
Chen, P ;
Cabrito, I ;
Moura, JJG ;
Moura, I ;
Solomon, EI .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (35) :10497-10507
[9]   Electronic structure description of the μ4-sulfide bridged tetranuclear Cuz center in N2O reductase [J].
Chen, P ;
George, SD ;
Cabrito, I ;
Antholine, WE ;
Moura, JJG ;
Moura, I ;
Hedman, B ;
Hodgson, KO ;
Solomon, EI .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (05) :744-745
[10]   Trinuclear intermediate in the copper-mediated reduction of O-2: Four electrons from three coppers [J].
Cole, AP ;
Root, DE ;
Mukherjee, P ;
Solomon, EI ;
Stack, TDP .
SCIENCE, 1996, 273 (5283) :1848-1850