0000000001310216
AUTHOR
Jeanet Conradie
Ligand Noninnocence in Cobalt Dipyrrin–Bisphenols: Spectroscopic, Electrochemical, and Theoretical Insights Indicating an Emerging Analogy with Corroles
Three cobalt dipyrrin-bisphenol (DPPCo) complexes with different meso-aryl groups (pentafluorophenyl, phenyl, and mesityl) were synthesized and characterized based on their electrochemistry and spectroscopic properties in nonaqueous media. Each DPPCo undergoes multiple oxidations and reductions with the potentials, reversibility, and number of processes depending on the specific solution conditions, the specific macrocyclic substituents, and the type and number of axially coordinated ligands on the central cobalt ion. Theoretical calculations of the compounds with different coordination numbers are given in the current study in order to elucidate the cobalt-ion oxidation state and the innoc…
Gold dipyrrin-bisphenolates: A combined experimental and DFT study of metal-ligand interactions
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 …
CCDC 1964008: Experimental Crystal Structure Determination
Related Article: Kolle E. Thomas, Nicolas Desbois, Jeanet Conradie, Simon J. Teat, Claude P. Gros, Abhik Ghosh|2020|RSC Advances|10|533|doi:10.1039/C9RA09228E
CCDC 1880078: Experimental Crystal Structure Determination
Related Article: Wenqian Shan, Nicolas Desbois, Sandrine Pacquelet, Stéphane Brandès, Yoann Rousselin, Jeanet Conradie, Abhik Ghosh, Claude P. Gros, Karl M. Kadish|2019|Inorg.Chem.|58|7677|doi:10.1021/acs.inorgchem.8b03006