Gold(I) complexes with redox active BIAN and MIAN ligands: synthesis, structure and electrochemistry

作者：Bardina, Elena E.; Shmelev, Nikita Y.; Albrekht, Yana N.; Koon, Winnie Ka Yiu; Abramov, Pavel A.; Mirzaeva, Irina V.; Sheven', Dmitriy G.; Makotchenko, Evgeniya V.; Fomenko, Iakov S.; Lukoyanov, Anton N.; Sokolov, Maxim N.; Babak, Maria V.^*; Gushchin, Artem L.^*

来源：New Journal of Chemistry, 2023, 47(39): 18251-18259.

DOI：10.1039/d3nj03334a

• HETEROCYCLIC CARBENE COMPLEXES
• INSERTION POLYMERIZATION
• SUBSTITUENTS
• APPROXIMATION
• COORDINATION
• REACTIVITY
• NICKEL
• BULKY

A series of cationic Au(i)-BIAN/MIAN complexes, namely [(PPh3)Au(L)]OTf, where L = dpp-bian (1), dpp-mian (2), 2-Me-Ph-bian (3) and 4-Me-Ph-bian (4), has been prepared. All complexes were characterized by analytical and spectroscopic methods and their crystal structures were determined by X-ray diffraction analysis. In all structures, an asymmetric mode of coordination of the di- or monoimine ligand (one shortened Au-N bond and the second elongated Au-N(O) bond) was found, which is a consequence of the so-called antichelate effect. The analysis of the bonding in the coordination environment of gold(i) and the coordination geometry in cations 1-4 was carried out using DFT calculations. The cyclic voltammograms of 1-4 in dichloromethane featured a series of ligand-centered redox processes in the cathodic region. Preliminary bioactivity tests for complexes 1-4 and respective imine ligands have been performed.