xotten at stanford dot edu Born in 1973, French. Ph.D. in Chemistry (Nov 2001), University of Paris-South, Orsay (France) Ferromagnetic couplers: Geometrical, topological and electrochemical considerations Advisors: Y. Journaux and A. Aukauloo Laboratoire de Chimie Inorganique   Member of Echoes of Fear and Black Horizon

Interests in the StackLab: Cu / O₂ chemistry.

Copper(I) complexes of peralkylated diamine ligands react quantitatively with dioxygen at low temperatures (193 K) to form Cu₂O₂ adducts: m-h²:h²-peroxodicopper(II) (P) and/or bis(m-oxo)dicopper(III) (O) isomers. Our goal is to study the conditions in which mixtures can form and the factors that govern the P / O ratio. In particular, we were able to show strong counteranion and solvents effects: P is favored with more coordinating anions and less polar solvents.
Beside these characterizations, the Cu₂O₂ species may be involved in reactivity experiments with external substrates, in order to get a better understanding of mechanistic pathways in enzymes like Tyrosinase working with the same kind of chemistry.
This challenging chemistry asks to handle very sensitive compounds. Anhydrous solvents, inert atmosphere and low temperatures are three necessary conditions in these experiments which are coupled with various spectroscopic techniques (UV-Vis, Resonance Raman, XAS, EXAFS).
 

Publications: (Click on the title to get the pdf file)

(21) Reversible O-O bond cleavage in copper-dioxygen isomers: impact of anion basicity
Ottenwaelder X., Jackson Rudd D., Corbett M.C., Hedman B., Hodgson K.O., Stack T.D.P.
J. Am. Chem. Soc.2006, 128, 29, 9268-9269.

(19) Bis(m-oxo)dicopper(III) Complexes of a Homologous Series of Simple Peralkylated 1,2-Diamines: Steric Modulation of Structure, Stability, and Reactivity
Cole A.P, Mahadevan V., Mirica L.M., Ottenwaelder X., Stack T.D.P.
Inorg. Chem. 2005, 44, 21, 7345-7364.

(12) Structure and spectroscopy of copper-dioxygen complexes
Mirica L.M., Ottenwaelder X., Stack T.D.P.
Chem. Rev.2004, 104, 2, 1013-1045.

(20) Synthesis, Structure, and Olefin Polymerization with Nickel(II) N-Heterocyclic Carbene Enolates
Ketz B.E., Ottenwaelder, X.G., Waymouth R.M.
Chem. Commun., 2005, 45, 5693?5695

(18) Molecular and electronic structure of square-planar nickel(II), nickel(III) and nickel(III)-cation radical complexes with a tetradentate o-phenylenedioxamidate redox-active ligand
Carrasco R., Cano J., Ottenwaelder X., Aukauloo A., Journaux Y., Ruiz-García R.
Dalton Trans. 2005, 15, 2527-2538.

(17) Synthesis, structure, spectroscopy and redox chemistry of square-planar nickel(II) complexes with tetradentate o-phenylenedioxamidates and related ligands
Ottenwaelder X., Aukauloo A., Journaux Y., Carrasco R., Cano J., Cervera B., Castro I., Curreli S., Muñoz M.C., Roselló A.L., Soto B., Ruiz-García R.
Dalton Trans. 2005, 15, 2516-2526.

(16) Magnetic anisotropy of a high-spin octanuclear nickel(II) complex with a meso-helicate core
Pardo E., Morales-Osorio I., Julve M., Lloret F., Cano J., Ruiz-Garcia R., Pasan J., Ruiz-Perez C., Ottenwaelder X., Journaux Y.
Inorg. Chem.2004, 43, 24, 7594-7596.

(15) Spin control in ladder-like hexanuclear copper(II) complexes with metallacyclophane cores
Pardo E., Bernot K., Julve M., Lloret F., Cano J., Ruiz-Garcia R., Delgado F.S., Ruiz-Perez C., Ottenwaelder X., Journaux Y.
Inorg. Chem.2004, 43, 9, 2768-2770.

(14) Self-assembly of a double-propeller octanuclear copper(II) complex with a meso helicate-type metallacryptand core
Pardo E., Bernot K., Julve M., Lloret F., Ruiz-Garcia R., Pasan J., Ruiz-Perez C., Ottenwaelder X., Journaux Y.
Chem. Commun.2004, 8, 920-921.

(13) From metal to ligand electroactivity in nickel(II) oxamato complexes
Ottenwaelder X., Ruiz-Garcia R., Blondin G., Carasco R., Cano J., Lexa D., Journaux Y., Aukauloo A.
Chem. Commun.2004, 5, 504-505.

(11) Rational design of an enneanuclear copper(II) complex with a metallacyclophane core
Ottenwaelder X., Cano J., Journaux Y., Rivière E., Brennan C., Nierlich M., Ruiz-Garcia R.
Angew. Chem., Int. Ed.2004, 43, 7, 850-852.

(10) Long-range magnetic coupling through extended p-conjugated aromatic bridges in dinuclear copper(II) metallacyclophanes
Pardo E., Faus J., Julve M., Lloret F., Muñoz M.C., Cano J, Ottenwaelder X., Journaux Y., Carrasco R., Blay G., Fernandez I., Ruiz-Garcia R.
J. Am. chem. Soc.2003, 125, 36, 10770-10771.

(9) A unique heterotopic ligand for sequential synthesis of polymetallic complexes
Berg K.E., Pellegrin Y., Blondin G., Ottenwaelder X., Journaux Y., Canovas M.M., Mallah T., Parsons S., Aukauloo A.
Eur. J. Inorg. Chem. 2002, 2, 323-325.

(8) Ferromagnetic coupling through spin polarization in a dinuclear copper(II) metallacyclophane
Fernandez I., Ruiz R., Faus J., Julve M., Lloret F., Cano J., Ottenwaelder X., Journaux Y., Muñoz M.C.
Angew. Chem., Int. Ed. 2001, 40, 16, 3039-3042.

(7) Alcohol oxidation by dioxygen and aldehydes catalysed by square-planar cobalt(III) complexes of disubstituted oxamides and related ligands
Fernandez I., Pedro J.R., Roselló A.L., Ruiz R., Castro I., Ottenwaelder X., Journaux Y.
Eur. J. Org. Chem. 2001, 7, 1235-1247.

(6) Rational design of homo and hetero hexanuclear coordination compounds: Syntheses and magnetic properties of [Cu^II₂M^II₄] (M = Cu ; Ni) species and the crystal structure of {[Cu(tmen)(H₂O)]₂[Cu(tmen)]₂[Cu₂L](H₂O)}(ClO₄)₂ · 2 H₂O
Aukauloo A., Ottenwaelder X., Ruiz R., Journaux Y., Pei Y., Rivière E., Muñoz M.C.
Eur. J. Inorg. Chem. 2000, 5, 951-957.

(5) An Na₈ cluster in the structure of a novel oxamato-bridged (Na^ICu^II) three-dimensional coordination polymer
Aukauloo A., Ottenwaelder X., Ruiz R., Journaux Y., Pei Y., Rivière E., Cervera B., Muñoz M.C.
Eur. J. Inorg. Chem. 1999, 2, 209-212.

(4) A square-planar dinickel(II) complex with a noninnocent dinucleating oxamate ligand: Evidence for a ligand radical species
Aukauloo A., Ottenwaelder X., Ruiz R., Poussereau S., Pei Y., Journaux Y., Fleurat P., Volatron F., Cervera B., Muñoz M.C.
Eur. J. Inorg. Chem. 1999, 7, 1067-1071.

(3) Stabilization of copper(III) complexes by substituted oxamate ligands
Cervera B., Sanz J.L., Ibanez M.J., Vila G., Lloret F., Julve M., Ruiz R., Ottenwaelder X., Aukauloo A., Poussereau S., Journaux Y., Muñoz M.C.
J. Chem. Soc., Dalton Trans. 1998, 5, 781-790.

(2) Aerobic epoxidation of olefins catalysed by square-planar nickel(II) complexes of bis-N,N'-disubstituted oxamides and related ligands
Fernandez I., Pedro J.R., Roselló A.L., Ruiz R., Ottenwaelder X., Journaux Y.
Tetrahedron Lett. 1998, 39, 18, 2869-2872.

(1) Aerobic epoxidation of olefins catalysed by square-planar cobalt(III) complexes of bis-N,N'-disubstituted oxamides and related ligands
Estrada J., Fernandez I., Pedro J.R., Ottenwaelder X., Ruiz R., Journaux Y.
Tetrahedron Lett. 1997, 38, 13, 2377-2380.