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Sulfur K-edge XAS and DFT Studies on NiII Complexes with Oxidized Thiolate Ligands: Implications for the Roles of Oxidized Thiolates in the Active Sites of Fe and Co Nitrile Hydratase

Fast O2 Binding at Dicopper Complexes Containing Schiff-Base Dinucleating Ligands

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Fast O2 Binding at Dicopper Complexes Containing Schiff-Base Dinucleating Ligands

Content Provider	PubMed Central
Author	Gómez, Laura Mas-ballesté, Rubén Korendovych, Ivan V. Ribas, Xavi Albert, Poater Parella, Teodor Fontrodona, Xavier Jordi, Benet-buchholz Miquel, Solà Que, Lawrence Elena, Rybak-akimova Costas, Miquel Company, Anna
Abstract	A new family of dicopper(I) complexes [CuI 2 RL](X)2, (R = H, 1X, R = tBu, 2X and R = NO2, 3X, X = CF3SO3, ClO4, SbF6 or BArF, BArF = [B{3,5-(CF3)2-C6H3}4]−), where RL is a Schiff-base ligand containing two tridentate binding sites linked by a xylyl spacer have been prepared, characterized, and their reaction with O2 studied. The complexes were designed with the aim of reproducing structural aspects of the active site of type 3 dicopper proteins; they contain two three-coordinate copper sites and a rather flexible podand ligand backbone. The solid state structures of 1ClO4 , 2CF3SO3 , 2ClO4 and 3BArF·CH3CN have been established by single crystal X-ray diffraction analysis. 1ClO4 adopts a polymeric structure in solution while 2CF3SO3 , 2ClO4 and 3BArF·CH3CN are monomeric. The complexes have been studied in solution by means of 1H and 19F NMR spectroscopy, which put forward the presence of dynamic processes in solution. 1-3BArF and 1-3CF3SO3 in acetone react rapidly with O2 to generate metaestable [CuIII 2(μ-O)2(RL)]2+ 1-3(O2) and [CuIII 2(μ-O)2(CF3SO3)(RL)]+ 1-3(O2)(CF3SO3) species, respectively that have been characterized by UV-vis spectroscopy and resonance Raman analysis. Instead, reaction of 1-3BArF with O2 in CH2Cl2 results in intermolecular O2 binding. DFT methods have been used to study the chemical identities and structural parameters of the O2 adducts, and the relative stability of the CuIII 2(μ-O)2 form with respect to the CuII 2(μ-η2: η2 -peroxo) isomer. The reaction of 1X, X = CF3SO3 and BArF with O2 in acetone has been studied by stopped-flow exhibiting an unexpected very fast reaction rate (k = 3.82(4) × 103 M−1s−1, ΔH ‡ = 4.9 ± 0.5 kJ·mol−1, ΔS ‡ = −148 ± 5 J·K−1·mol−1), nearly three orders of magnitude faster than in the parent [CuI 2(m-XYLMeAN)]2+. Thermal decomposition of 1-3(O2) does not result in aromatic hydroxylation. The mechanism and kinetics of O2 binding to 1X (X = CF3SO3 and BArF) is discussed and compared with those associated to selected examples of reported models of O2-processing copper proteins. A synergistic role of the copper ions in O2 binding and activation is clearly established from this analysis.
Related Links	http://dx.doi.org/10.1021/ic0701108
Ending Page	5012
Page Count	16
Starting Page	4997
File Format	PDF
ISSN	00201669
e-ISSN	1520510X
Journal	Inorganic chemistry
Issue Number	12
Volume Number	46
Language	English
Publisher Date	2007-06-01
Access Restriction	Open
Subject Keyword	Physical and Theoretical Chemistry Inorganic Chemistry Research in Higher Education
Content Type	Text
Resource Type	Article
Subject	Physical and Theoretical Chemistry Inorganic Chemistry

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