Gold dipyrrin-bisphenolates: a combined experimental and DFT study of metal–ligand interactions. Issue 1 (2nd January 2020)

• Record Type: Journal Article
• Authors: Thomas, Kolle E.; Desbois, Nicolas; Conradie, Jeanet; Teat, Simon J.; Gros, Claude P.; Ghosh, Abhik
• Is Part Of: RSC advances. Volume 10:Issue 1(2020)
• Page Start: 533
• Page End: 540
• Publication Date: 2020-01-02
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c9ra09228e
• Languages: English
• ISSNs: 2046-2069

Abstract

Abstract : The first gold dipyrrin-bisphenolates have been synthesized. Like their corrole analogues, they exhibit Au III –L 3− ground states, providing rare innocent paradigms for a class of complexes that commonly occur as metalloradicals. Abstract : 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 Au III –DPP 3−, 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.