3 years ago

Group 11 Metal Complexes Coordinated by (Nitronyl Nitroxide)-2-ide Radical Anion: Facile Oxidation of Stable Radicals Controlled by MetalCarbon Bonds in Radical-Metalloids

Masatoshi Kozaki, Kiyomi Yamada, Shuichi Suzuki, Ryu Tanimoto, Keiji Okada
A series of group 11 metal complexes coordinated by (nitronyl nitroxide)-2-ide radical anions (NNM(dtpb) (NN: nitronyl nitroxide; M: Cu(I), Ag(I), and Au(I); dtpb: 1,2-bis(di-2-tolylphosphino)benzene)) was prepared. Their structures, electrochemical properties, and related theoretical calculations were investigated. The oxidation potential (Eox, V vs Fc/Fc+) of the NN-moiety in these radical-metalloids significantly shifted to the negative direction in comparison to that of the unsubstituted nitronyl nitroxide (NNH, Eox=+0.38 V) and strongly depended on the metal ion (Eox=-0.37 V for M=Cu(I), -0.31 V for Ag(I), and -0.28 V for Au(I)). The Eox values correlated with the energy level of the HOMO (SOMO) and also with the natural atomic charge of the C2 carbon atom attached to the metal ion, indicating that the ionic character of the metal-C2-carbon bond is a key factor in controlling the oxidation potential of these radical metalloids.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/ejic.201800038

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