Azo-oximate metal-carbonyl to metallocarboxylic acid via the intermediate Ir(iii) radical congener: quest for co-ligand driven stability of open- and closed-shell complexes. Issue 26 (22nd June 2022)

• Record Type: Journal Article
• Authors: Dinda, Soumitra; Pramanik, Shuvam; Basu, Jaydeep; Patra, Sarat Chandra; Pramanik, Kausikisankar; Ganguly, Sanjib
• Is Part Of: Dalton transactions. Volume 51:Issue 26(2022)
• Page Start: 10121
• Page End: 10135
• Publication Date: 2022-06-22
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d2dt00345g
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Radical-mediated conversion of metal carbonyl to metallocarboxylic acid has been successfully accomplished along with the exploration of the stability of open- and closed-shell complexes by stereochemical alteration of co-ligands. Abstract : The redox non-innocent behavior of the diaryl-azo-oxime ligand L NOH 1 has been accentuated via the synthesis of metastable anion radical complexes of type trans -[Ir(L NO ˙− )Cl(CO)(PPh3 )2 ] 2 (CO is trans to azo group of the ligand) by the oxidative coordination reaction of 1 with Vaska's complex. The stereochemical role of co-ligands vis-à-vis the interplay of π-bonding has been found to be decisive in controlling the aptitude of the coordinated redox non-innocent ligand to accept or reject an electron. This has been clarified via the isolation of quite a few complexes as well as the failure to synthesize some others. The oxidized analogues of type trans -[Ir(L NO− )Cl(CO)(PPh3 )2 ] + 2 + (CO and azo group of the ligand are trans ) as well as its cis isomer cis -[Ir(L NO− )Cl(CO)(PPh3 )2 ] + 3 + (CO and azo group of the ligand are cis ) have been structurally characterized but the radical anion congener of the latter could not be synthesized. Furthermore, the closed shell complexes [Ir(L NO− )Cl2 (PPh3 )2 ] 4 and [Ir(L NO− )2 Cl(PPh3 )] 5 have been well characterized by diffraction as well as spectral techniques but their corresponding azo anion radical complexes could not be isolated and this is attributed to the trans influence of ancillary ligands. The anion radical complexes trans -[Ir(L NO˙− )Cl(CO)(PPh3 )2 ] 2 may be rapidly transformed to the metallocarboxylic acids trans -[Ir(L NO− )Cl(CO2 H)(PPh3 )2 ] 6 via a proton-coupled electron transfer (PCET) process, thereby demonstrating the role of odd electron over the coordinated ligand framework to trigger metal-mediated carbonyl to carboxylic acid functionalization. Complexes 6 are further stabilized via intramolecular –CO2 H⋯ON− (carboxylic acid⋯oximato) H-bonding. The optoelectronic properties as well as the origin of transitions in the complexes were analyzed by TD-DFT and theoretical analysis, which further disclose that the odd electron in trans -[Ir(L NO˙− )Cl(CO)(PPh3 )2 ] 2 is primarily azo-oxime centric with very low contribution from the iridium center.