Trinuclear, antiferromagnetically coupled CuII complex with an EPR spectrum of mononuclear CuII:: Effect of alcoholic solvents

被引:43
作者
Mezei, Gellert
Raptis, Raphael G. [1 ]
Telser, Joshua
机构
[1] Univ Puerto Rico, Dept Chem, San Juan, PR 00931 USA
[2] Roosevelt Univ, Dept Biol Chem & Phys Sci, Chicago, IL 60605 USA
关键词
D O I
10.1021/ic061186r
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A rigid trinuclear copper pyrazolato framework supports the solvolytic exchange of mu(3)-X by mu(3)-OR ligands ( X= Cl and Br; R) alkyl group), converting the trinuclear ferromagnetically coupled S = 3/2 system to antiferromagnetically coupled S = 1/2 in the solid state. In contrast, we propose that, in alcoholic solutions, solvolysis results in unsymmetrical coordination of the Cu-3 cluster, magnetically decoupling one Cu center from the other two. This disguises the intact triangular Cu-3(II) system as a mononuclear Cu-II complex in its electron paramagnetic resonance spectrum.
引用
收藏
页码:8841 / 8843
页数:3
相关论文
共 14 条
[1]   Synthesis and structural characterization of trinuclear CuII-pyrazolato complexes containing μ3-OH, μ3-O, and μ3-Cl ligands.: Magnetic susceptibility study of [PPN]2[(μ3-O)Cu3(μ-pz)3Cl3] [J].
Angaridis, PA ;
Baran, P ;
Boca, R ;
Cervantes-Lee, F ;
Haase, W ;
Mezei, G ;
Raptis, RG ;
Werner, R .
INORGANIC CHEMISTRY, 2002, 41 (08) :2219-2228
[2]   Hyperfine splittings in spin-frustrated trinuclear Cu3 clusters [J].
Belinsky, MI .
INORGANIC CHEMISTRY, 2004, 43 (02) :739-746
[3]   Triangular, ferromagnetically-coupled CuII3-pyrazolato complexes as possible models of particulate methane monooxygenase (pMMO) [J].
Boca, R ;
Dlhán, L ;
Mezei, G ;
Ortiz-Pérez, T ;
Raptis, RG ;
Telser, J .
INORGANIC CHEMISTRY, 2003, 42 (19) :5801-+
[4]  
LEMOS SS, 2002, CURR TOP BIOPHYS, V26, P43
[5]   Crystal structure of a membrane-bound metalloenzyme that catalyses the biological oxidation of methane [J].
Lieberman, RL ;
Rosenzweig, AC .
NATURE, 2005, 434 (7030) :177-182
[6]   Antisymmetric exchange in two tricopper(II) complexes containing a [Cu3(μ3-OMe)]5+ core [J].
Liu, XM ;
de Miranda, MP ;
McInnes, EJL ;
Kilner, CA ;
Halcrow, MA .
DALTON TRANSACTIONS, 2004, (01) :59-64
[7]  
Messerschmidt A, 1998, STRUCT BOND, V90, P37
[8]   The particulate methane monooxygenase from methylococcus capsulatus (Bath) is a novel copper-containing three-subunit enzyme -: Isolation and characterization [J].
Nguyen, HHT ;
Elliott, SJ ;
Yip, JHK ;
Chan, SI .
JOURNAL OF BIOLOGICAL CHEMISTRY, 1998, 273 (14) :7957-7966
[9]  
NGUYEN HHT, 1994, J BIOL CHEM, V269, P14995
[10]   X-ray absorption and EPR studies on the copper ions associated with the particulate methane monooxygenase from Methylococcus capsulatus (Bath). Cu(I) ions and their implications [J].
Nguyen, HHT ;
Nakagawa, KH ;
Hedman, B ;
Elliott, SJ ;
Lidstrom, ME ;
Hodgson, KO ;
Chan, SI .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (50) :12766-12776