PMID- 17140245
OWN - NLM
STAT- MEDLINE
DCOM- 20070207
LR  - 20131121
IS  - 0020-1669 (Print)
IS  - 0020-1669 (Linking)
VI  - 45
IP  - 25
DP  - 2006 Dec 11
TI  - Multifrequency EPR and redox reactivity investigations of a 
      bis(mu-thiolato)-dicopper(II,II) complex.
PG  - 10355-62
AB  - From a new tripodal ligand [N2SS'H] with mixed N, S(thioether), and S(thiolate) 
      donor set, the corresponding bis(mu-thiolato)dicopper(II) complex has been 
      prepared and characterized. X-ray crystallographic analysis of the complex 
      [Cu2(N2SS')2](ClO4)2.C4H10O (1) demonstrates that the two five-coordinated Cu 
      atoms are bridged by two thiolates leading to a nearly planar Cu2S2 core with a 
      Cu1...Cu1* distance of 3.418(8) A and a large bridging angle Cu1S1Cu1* of 94.92 
      degrees. X-band (10 GHz), Q-band (34 GHz), and F-Band (115 GHz) EPR spectra of 1 
      are consistent with a weakly coupled dicopper(II,II) center attributed to an S = 
      1 state. Simulations for the three frequencies are obtained with a unique set of 
      electronic parameters. The mean values of the spin Hamiltonian parameters for 1 
      are D = 0.210(3) cm(-1), E = 0.0295(5) cm(-1), |E/D| = 0.140, gx = 2.030(2), gy = 
      2.032(2), gz = 2.128(2). The electrochemical one-electron reduction of 1 
      generates the mixed-valent CuIICuI species. EPR and UV-vis spectra are consistent 
      with a type I localized mixed-valent species, while dinuclear CuA centers of 
      native cytochrome c oxidase (CcO)1-3 or nitrous oxide reductase (N2OR)4 have a 
      delocalized CuIICuI mixed-valent state. After reoxidation of the CuIICuI species, 
      the initial complex 1 is regenerated through a reversible interconversion 
      process.
FAU - Rammal, Wassim
AU  - Rammal W
AD  - Laboratoire de Chimie Biomimetique, UMR CNRS 5616, ICMG FR CNRS 2607, BP 53X, 
      38041 Grenoble Cedex 9, France.
FAU - Belle, Catherine
AU  - Belle C
FAU - Beguin, Claude
AU  - Beguin C
FAU - Duboc, Carole
AU  - Duboc C
FAU - Philouze, Christian
AU  - Philouze C
FAU - Pierre, Jean-Louis
AU  - Pierre JL
FAU - Le Pape, Laurent
AU  - Le Pape L
FAU - Bertaina, Sylvain
AU  - Bertaina S
FAU - Saint-Aman, Eric
AU  - Saint-Aman E
FAU - Torelli, Stephane
AU  - Torelli S
LA  - eng
PT  - Journal Article
PL  - United States
TA  - Inorg Chem
JT  - Inorganic chemistry
JID - 0366543
RN  - 0 (Organometallic Compounds)
RN  - 0 (Sulfhydryl Compounds)
RN  - 789U1901C5 (Copper)
RN  - EC 1.- (Oxidoreductases)
RN  - EC 1.7.2.4 (nitrous oxide reductase)
RN  - EC 1.9.3.1 (Electron Transport Complex IV)
SB  - IM
MH  - Catalysis
MH  - Copper/*chemistry
MH  - Crystallography, X-Ray/methods
MH  - Electron Spin Resonance Spectroscopy/methods
MH  - Electron Transport Complex IV/chemistry/metabolism
MH  - Hydrogen-Ion Concentration
MH  - Organometallic Compounds/*chemistry
MH  - Oxidation-Reduction
MH  - Oxidoreductases/chemistry/metabolism
MH  - Spectrophotometry, Ultraviolet/methods
MH  - Sulfhydryl Compounds/*chemistry
EDAT- 2006/12/05 09:00
MHDA- 2007/02/08 09:00
CRDT- 2006/12/05 09:00
PHST- 2006/12/05 09:00 [pubmed]
PHST- 2007/02/08 09:00 [medline]
PHST- 2006/12/05 09:00 [entrez]
AID - 10.1021/ic0612606 [doi]
PST - ppublish
SO  - Inorg Chem. 2006 Dec 11;45(25):10355-62. doi: 10.1021/ic0612606.