Stabilisation of a highly reactive bis(mu-oxo)dicopper(III) species at room temperature by electronic and steric constraint of an unconventional nitrogen donor ligand.

Herein we present an innovative combination of EXAFSspectroscopy and resonant Raman scattering for the charac-terisation of the ground state and structural dynamics of athermally stable binuclear bisACHTUNGRE(m-oxo) dicopperACHTUNGRE(III) species.Peralkylated bis(guanidine)-based ligands are used in thesynthesis of this compound.

[1]  T. Ressler WinXAS: a program for X-ray absorption spectroscopy data analysis under MS-Windows. , 1998, Journal of synchrotron radiation.

[2]  William B Tolman,et al.  Reactivity of dioxygen-copper systems. , 2004, Chemical reviews.

[3]  R. Strange,et al.  Constrained and restrained refinement in EXAFS data analysis with curved wave theory. , 1992, Biochemistry.

[4]  I. Ascone,et al.  Experimental aspects of biological X-ray absorption spectroscopy. , 2003, Journal of synchrotron radiation.

[5]  Jason A. Halfen,et al.  Reversible Cleavage and Formation of the Dioxygen O-O Bond Within a Dicopper Complex , 1996, Science.

[6]  Edward I. Solomon,et al.  Spectroscopic and Electronic Structural Studies of the Cu(III)2 Bis-μ-oxo Core and Its Relation to the Side-On Peroxo-Bridged Dimer , 1999 .

[7]  W. Woodruff,et al.  Detailed aspects of Raman scattering. Overtone and combination intensities and prescriptions for determining excited-state structure , 1985 .

[8]  M. Korbas,et al.  KEMP: A program script for automated biological x-ray absorption spectroscopy data reduction , 2006 .

[9]  Miles V. Klein,et al.  Fully reflective deep ultraviolet to near infrared spectrometer and entrance optics for resonance Raman spectroscopy , 2005 .

[10]  U. Flörke,et al.  Hydroxylation of a methyl group : synthesis of [Cu2(btmmo)2I]+ and of [Cu2(btmmO)2]2+ containing the novel ligand {bis(trimethylmethoxy)guanidino} propane (btmmO) by copper-assisted oxygen activation , 2005 .

[11]  P. Holland,et al.  Dioxygen activation by copper sites: relative stability and reactivity of (μ-η2:η2-peroxo)- and bis(μ-oxo)dicopper cores , 1999 .

[12]  J. J. Schneider,et al.  1,3-Bis(N,N,N′,N′-tetramethylguanidino)propane: synthesis, characterization and bonding properties of the first bidentate, peralkylated guanidine ligand , 2000 .

[13]  Christian Würtele,et al.  Reactions of a copper(II) superoxo complex lead to C-H and O-H substrate oxygenation: modeling copper-monooxygenase C-H hydroxylation. , 2008, Angewandte Chemie.

[14]  Edward I. Solomon,et al.  Kupferproteine: Koordination und Aktivierung von Sauerstoff und seine Reduktion zu Wasser , 2001 .

[15]  Bart Hazes,et al.  Crystallographic analysis of oxygenated and deoxygenated states of arthropod hemocyanin shows unusual differences , 1994, Proteins.

[16]  T. D. Stack,et al.  Complexity with simplicity: a steric continuum of chelating diamines with copper(I) and dioxygen , 2003 .

[17]  Jan Reedijk,et al.  Homogeneous biomimetic oxidation catalysis , 2006 .

[18]  Y. Matoba,et al.  Crystallographic Evidence That the Dinuclear Copper Center of Tyrosinase Is Flexible during Catalysis* , 2006, Journal of Biological Chemistry.

[19]  U. Fittschen,et al.  Optimizing total reflection X-ray fluorescence for direct trace element quantification in proteins I: Influence of sample homogeneity and reflector type☆ , 2008 .

[20]  E. Heller,et al.  Polyatomic Raman scattering for general harmonic potentials , 1982 .

[21]  Sonja Herres-Pawlis,et al.  A Library of Peralkylated Bis‐guanidine Ligands for Use in Biomimetic Coordination Chemistry , 2005 .

[22]  Michael Vance,et al.  Tyrosinase Reactivity in a Model Complex: An Alternative Hydroxylation Mechanism , 2005, Science.

[23]  K. V. van Holde,et al.  Crystal structure of a functional unit from Octopus hemocyanin. , 1998, Journal of molecular biology.

[24]  T. Keil Shapes of Impurity Absorption Bands in Solids , 1965 .

[25]  K. Hodgson,et al.  A Systematic K-edge X-ray Absorption Spectroscopic Study of Cu(III) Sites , 2000 .

[26]  Adam P. Cole,et al.  Bis(mu-oxo)dicopper(III) complexes of a homologous series of simple peralkylated 1,2-diamines: steric modulation of structure, stability, and reactivity. , 2005, Inorganic chemistry.

[27]  K. Karlin,et al.  Copper-dioxygen complexes and their roles in biomimetic oxidation reactions , 2003 .

[28]  E. Heller,et al.  Time‐dependent theory of Raman scattering , 1979 .

[29]  W. Tolman,et al.  Bis(μ‐oxo)dimetal “Diamond” Cores in Copper and Iron Complexes Relevant to Biocatalysis , 2002 .

[30]  J. Carpenter,et al.  Recent Structural Work on the Oxygen Transport Protein Hemocyanin , 1994 .

[31]  Sonja Herres-Pawlis,et al.  Tuning of Copper(I)–Dioxygen Reactivity by Bis(guanidine) Ligands , 2005 .

[32]  T. D. Stack,et al.  Structure and spectroscopy of copper-dioxygen complexes. , 2004, Chemical reviews.

[33]  Siegfried Schneider,et al.  Combined spectroscopic and theoretical evidence for a persistent end-on copper superoxo complex. , 2004, Angewandte Chemie.

[34]  A. Palmer,et al.  Oxygen Binding, Activation, and Reduction to Water by Copper Proteins. , 2001, Angewandte Chemie.

[35]  William B. Tolman,et al.  Biokatalytisch relevante rautenförmige Bis(μ‐oxo)dimetall‐Kerne in Kupfer‐ und Eisenkomplexen , 2002 .

[36]  Siegfried Schneider,et al.  Spektroskopischer und theoretischer Nachweis eines beständigen End‐on‐Kupfersuperoxokomplexes , 2004 .

[37]  Patrick L. Holland,et al.  Resonance Raman spectroscopy as a probe of the bis(μ-oxo)dicopper core , 2000 .

[38]  Sonja Herres-Pawlis,et al.  Phenolate hydroxylation in a bis(mu-oxo)dicopper(III) complex: lessons from the guanidine/amine series. , 2009, Journal of the American Chemical Society.

[39]  Klaus Harms,et al.  Crystallographic characterization of a synthetic 1:1 end-on copper dioxygen adduct complex. , 2006, Angewandte Chemie.

[40]  K. Harms,et al.  Kristallographische Charakterisierung eines synthetischen 1:1-End-on-Kupferdisauerstoff- Adduktkomplexes† , 2006 .

[41]  William B. Tolman,et al.  Copper-Dioxygen and Copper-Oxo Species Relevant to Copper Oxygenases and Oxidases , 2000 .