The use of transition metal catalysts expanded the scope of reactivity of organic compounds due to the
ability of transition metals to participate in various reaction types, such as oxidative addition, reductive
elimination and β-hydride elimination. Such transformations occur at the metal center, while the ligands
remain unchanged over the course of the reaction. However, the metal-ligand cooperation, in which both
the metal and ligand participate in bond cleavage and formation is gathering great attention lately. [1]
Recently, cooperation between transition metal and E-H (E = H, B, Si, C) bonds has emerged great interest
due to their intervening property in chemical reactivity. [2] For example, boranes and silanes are captured
or splitted by an adjacent Lewis basic ligand at the transition metal center and thus, they have been
utilized in various catalytic processes, like hydroboration, [2] hydrosilylation [2] reactions. In this seminar,
the synthesis, properties and applications of various complexes which shows metal-ligand cooperation as
well as preliminary result of my research work in this field will be discussed.
Scheme 1. Metal-Ligand Cooperation
References:
[1]. (a) H. Grützmacher, Angew. Chem. Int. Ed., 2008, 47, 18141818; (b) J. R. Khusnutdinova, D. Milstein, Angew. Chem. Int.
Ed., 2015, 54, 12236 12273; (c) T. Higashi, S. Kusumoto, K. Nozaki, Chem. Rev., 2019, 119, 10393−10402; (d) R. Peters,
Cooperative Catalysis, Wiley-VCH: Weinheim, 2015.
[2]. (a) J. B. Geri, N. K. Szymczak, J. Am. Chem. Soc., 2015, 137, 12808-12814; (b) M. W. Drover, L. L. Schafer, J. A. Love, Angew.
Chem. Int. Ed., 2016, 55, 3181-3186; (c) T. Stahl, P. Hrobarik, C. D. F. Konigs, Y. Ohki, K. Tatsumi, S. Kemper, M. Kaupp, H.
F. T. Klare, M. Oestreich, Chem. Sci., 2015, 6, 4324-4334. (d) T. Stahl, K. Mether, Y. Ohki, K. Tatsumi, M. Oestreich, J. Am.
Chem. Soc., 2013, 135, 10978-10981. (e) J.Y. Corey, Chem. Rev., 2011, 111, 863-1071. (f) Y. Nakajima, S. Shimada, RSC
Adv., 2015, 5, 20603-20616.