AUTHOR=Sengupta Poulami , Das Rituparna , Dhibar Papu , Paul Piyali , Bhattacharya Samaresh 

TITLE=Rhodium and Iridium Mediated C-H and O-H Bond Activation of Two Schiff Base Ligands: Synthesis, Characterization and Catalytic Properties of the Organometallic Complexes

JOURNAL=Frontiers in Chemistry

VOLUME=9

YEAR=2021

URL=https://www.frontiersin.org/journals/chemistry/articles/10.3389/fchem.2021.696460

DOI=10.3389/fchem.2021.696460

ISSN=2296-2646

ABSTRACT=<p>Reaction of [Rh(PPh<sub>3</sub>)<sub>3</sub>Cl] with two Schiff base ligands, <italic>viz</italic>. N-(2′-hydroxyphenyl)furan-2-aldimine (<bold>H</bold><sub><bold>2</bold></sub><bold>L</bold><sup><bold>1</bold></sup>) and N-(2′-hydroxyphenyl)thiophene-2-aldimine (<bold>H</bold><sub><bold>2</bold></sub><bold>L</bold><sup><bold>2</bold></sup>), in refluxing toluene affords organorhodium complexes of type [Rh(PPh<sub>3</sub>)<sub>2</sub>(L)Cl] (L = L<sup>1</sup> and L<sup>2</sup>). Similar reaction with [Ir(PPh<sub>3</sub>)<sub>3</sub>Cl] yields organoiridium complexes of type [Ir(PPh<sub>3</sub>)<sub>2</sub>(L) (H)] (L = L<sup>1</sup> and L<sup>2</sup>). Crystal structures of [Rh(PPh<sub>3</sub>)<sub>2</sub>(L<sup>1</sup>)Cl] and [Ir(PPh<sub>3</sub>)<sub>2</sub>(L<sup>2</sup>) (H)] have been determined, where the imine ligands are found to bind to the metal centers as CNO-donors. Structures of [Rh(PPh<sub>3</sub>)<sub>2</sub>(L<sup>2</sup>)Cl] and [Ir(PPh<sub>3</sub>)<sub>2</sub>(L<sup>1</sup>) (H)] have been optimized by density functional theory method. Formation of the organometallic complexes is believed to proceed via C-H and O-H bond activation of the imine ligands. All four complexes show intense absorptions in the visible and ultraviolet regions. Cyclic voltammetry on the complexes shows an oxidation on the positive side of SCE and a reduction on the negative side. The organoiridium complexes are found to efficiently catalyze Suzuki-type C-C cross coupling reactions.</p>