Yuichi Shimazaki has received his Doctorate degree in Science from Nagoya University in 2000 under the supervision of Professor Osamu Yamauchi. He joined Professor Yoshinori Naruta’s group at Kyushu University as Assistant Professor and worked on the redox behavior of various metal porphyrin complexes as models of the active site of metalloenzymes. In 2008, he was promoted to Associate Professor at the College of Science, Ibaraki University. His research interests include the oxidation chemistry of the complexes of various metal ions, model studies of metalloenzymes, bioorganometallic chemistry, and weak interactions in metalorganic

molecule systems.

Chemistry of redox active transition metal complexes with pro-radical ligands and their detailed electronic structures have been actively pursued in recent years. An “experimental” valence state in metal complexes is sometime different from the “formal” oxidation state, especially in the species having redox active ligands. This difference can be also seen in biological system, such as iron(IV)-porphyrin p-cation radical in some heme proteins and copper(II)-phenoxyl radical in galactose oxidase (GO). Many efforts for determination of the experimental oxidation number have been close to the goal of the “truth oxidation state” in various oxidized metal complexes with redox-active ligands. Depending on the relative energies of the redoxactive orbitals, metal complexes with the redox active ligands exist in two limiting descriptions, either a metal-ligand radical (Mn+(L•)) or a high valent metal (M(n+1)+(L-)) complex. The reaction mechanisms of artificial and biological catalysts depend on the electronic structures of the high valent intermediates. However, geometric and electronic structural characterizations of the high valent species have been rare due to their stability. Recently, some artificial metal−phenoxyl radical complexes as models of GO have been synthesized and successfully characterized by X-ray crystal structure. The one-electron oxidized metal-phenolate complexes showed various electronic structures depending on small perturbations, such as substitution of the phenolate ring and the chelate effect of the phenolate ligands and so on. In this presentation, I will focus on X-ray crystal structures of the oneand two-electron oxidized metal(II)–phenolate complexes (Ni(II), Pd(II), Pt(II) and Cu(II)) with Schiff base ligands of 2N2O donor sets. Especially electronic and geometric structure relationship such as differences of metal-phenoxyl radical and highvalent metal phenolate complexes, and the effect of different oxidation locus of the radical electron on the ligands in oxidized forms will be discussed.

Virginie Vidal obtained her Ph.D from Paris Sud University. She then pursued postdoctoral appointments in the University of Montreal (Canada). She is currently CNRS Research Director at Chimie ParisTech in Paris. Her research interests focus on transition-metal catalysis, metalloorganocatalysis and organic synthesis. The synthesis of bio-relevant targets is also a focus in her group. She was Chair of the Division of Organic Chemistry of the French Chemical Society (2009-2012). She has published more than 150 papers in reputed journals, chapters and patents and has been serving as a board member of EuCheMS Division of Organic Chemistry since 2010.

Over the past few years, significant research has been directed toward the development of new methods for synthetic efficiency and atom economical processes. Among them, the potential of transition metal-catalyzed reactions has been steadily demonstrated, as they provide a direct and selective way toward the synthesis of highly valuable products. We focus on the development of catalytic methods for the synthesis of bio-relevant targets. More specifically, we have been interested in hydrogenation and transfer hydrogenation reactions, which provide important catalytic approaches to fine chemicals. There is no doubt that chiral ligands are at the heart of any enantioselective homogeneous process. In this context, our contribution to this field is the development of atropisomeric diphosphanes named SYNPHOS and DIFLUORPHOS with complementary stereoelectronic properties. Some applications in organic chemistry will be presented.