Lawrence Berkeley National Laboratory
Gold dipyrrin-bisphenolates: A combined experimental and DFT study of metal-ligand interactions
- Author(s): Thomas, KE
- Desbois, N
- Conradie, J
- Teat, SJ
- Gros, CP
- Ghosh, A
- et al.
Published Web Locationhttps://doi.org/10.1039/c9ra09228e
This journal is © The Royal Society of Chemistry. Given that noninnocent and metalloradical-type electronic structures are ubiquitous among dipyrrin-bisphenolate (DPP) complexes, we synthesized the gold(iii) derivatives as potentially innocent paradigms against which the properties of other metallo-DPP derivatives can be evaluated. Electronic absorption spectra, electrochemical studies, a single-crystal X-ray structure, and DFT calculations all suggest that the ground states of the new complexes indeed correspond to an innocent AuIII-DPP3-, paralleling a similar description noted for Au corroles. Interestingly, while DFT calculations indicate purely ligand-centered oxidations, reduction of AuDPP is predicted to occur across both the metal and the ligand.