A Diruthenium Complex of an N‐Pyridyl‐o‐aminophenol Derivative: A Route to Mixed Valency. Issue 65 (24th October 2019)

• Record Type: Journal Article
• Authors: Dutta, Debarpan; Kundu, Suman; Ghosh, Prasanta
• Is Part Of: Chemistry. Volume 25:Issue 65(2019)
• Page Start: 14901
• Page End: 14911
• Publication Date: 2019-10-24
• Subjects: bridging ligands -- charge transfer -- mixed-valent compounds -- redox chemistry -- ruthenium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201903028
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: An N ‐pyridyl‐ o ‐aminophenol derivative that stabilises mixed‐valence states of ruthenium ions is disclosed. A diruthenium complex, [(LIQ 0 )Ru2 Cl5 ]⋅ MeOH (1⋅ MeOH) is successfully isolated, in which LIQ 0 is the o ‐iminobenzoquinone form of 2‐[(3‐nitropyridin‐2‐yl)amino]phenol (LAP H2 ). In 1, LIQ 0 oriented towards one ruthenium centre is a non‐innocent NO‐donor redox ligand, whereas another oriented towards another ruthenium centre is an innocent pyridine‐donor redox ligand. Complex 1 is a diruthenium(II, III) mixed‐valence complex, [Ru II (LIQ 0 )(μ‐Cl)2 Ru III ], with a minor contribution from the diruthenium(III, III) state. [Ru III (LISQ .− )(μ‐Cl)2 Ru III ] contains LISQ .−, which is the o ‐iminobenzosemiquinonate anion radical form of the ligand. Complexes 1 − and 1 + are diruthenium(II, II), [Ru II (LIQ 0 )(μ‐Cl)2 Ru II ], and diruthenium(III, III), [Ru III (LIQ 0 )(μ‐Cl)2 Ru III ], complexes, respectively, of LIQ 0 . Complex 1 2− is a diruthenium(II, II) complex of the o ‐iminobenzosemiquinonate anion radical (LISQ .− ), [Ru II (LISQ .− )(μ‐Cl)2 Ru II ], with a minor contribution from the diruthenium(III, II) form, [Ru III (LAP 2− )(μ‐Cl)2 Ru II ]. Complex 1 2+ is a diruthenium(III, IV) mixed‐valence complex of LIQ 0, [Ru III (LIQ 0 )(μ‐Cl)2 Ru IV ]. Complexes 1 and 1 2+ exhibit inter‐valence charge‐transfer transitions at λ =1300 and 1370 nm, respectively. Abstract : Innocent or not? A diruthenium complex, [(LIQ 0 )Ru2 Cl5 ]⋅ MeOH (1⋅ MeOH) was isolated, where LIQ 0 is the o ‐iminobenzoquinone form of 2‐((3‐nitropyridin‐2‐yl)amino)phenol (LAP H2 ). In 1, LIQ 0 oriented towards one ruthenium centre is a NO‐donor redox non‐innocent, whereas towards another ruthenium it is a pyridine donor redox innocent ligand and the stabilisations of the states [Ru III (LIQ 0 )(μ‐Cl)2 Ru IV ], [Ru III (LIQ 0 )(μ‐Cl)2 Ru III ], [Ru II (LIQ 0 )(μ‐Cl)2 Ru III ], [Ru II (LIQ 0 )(μ‐Cl)2 Ru II ] and [Ru II (LISQ .− )(μ‐Cl)2 Ru II ] are reported.