Non‐Spectator Feature of α‐Diimine Mimicked Di/tetrahydro‐bisisoquinoline and Biimidazopyridine on {Ru(acac)<sub>2</sub>} Platform

Panda, Sanjib; Goel, Puneet; Lahiri, Goutam Kumar

doi:10.1002/ejic.202000230

Cited by 9 publications

(3 citation statements)

References 85 publications

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“…(ii) Metal based reversible oxidation (Ru II →Ru III ) and ligand (L2′) based irreversible reduction of 2 [14] . (iii) Low Ru(II)/Ru(III) potential of 2 (0.11 V versus SCE) facilitated the isolation of Ru III −L2′ congener ( 2 + ) by AgClO 4 oxidant [14c–d] . (iv) Metal based reversible oxidation (Ru III →Ru IV ) and reduction (Ru III →Ru II ) in 3 as reported earlier [5] …”

Section: Resultssupporting

confidence: 57%

Redox Induced Tunable Functionalization of Picolylamines on Selective Ru‐Platform

et al. 2020

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Redox induced ligand centered reactivity has garnered significant attention in recent times. In this context, the present article described intermolecular oxygenation, dehydrogenation and C−N bond cleavage processes of structurally robust picolylamine derivatives (HL) on selective {Ru(acac)2} metal platform encompassing electron rich acac (=acetylacetonate) co‐ligand. The diverse functionalization of {Ru(acac)2} coordinated β‐ketoiminate embedded picolylamines under basic condition included (i) oxygenation of methylene (Cα) position of picolyl fragment (−CH2−NH−→−CO−NH−), (ii) dehydrogenation of phenyl substituted Cα (−CH−NH−→−C=N−) and (iii) C−N bond cleavage of the picolinoyl moiety to yield picolinate (−CO−N−−→−CO−O−). Besides structural, spectroscopic (mass, 1H/13C−NMR, EPR, UV‐vis.) and electrochemical authentication of the products, correlation of the reactivity pattern was addressed via transition state (TS) calculations. Theoretical results supported the consideration of a common dianionic intermediate to address the aforementioned reactivities. The pertinent question of intramolecular cyclization versus intermolecular oxygenation of picolylamine on simple switching from {Ru(Cl)(H)(CO)(PPh3)3} (earlier work[4a]) metal fragment to {Ru(acac)2} (present report) was also elaborated by TS calculation.

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Section: Resultssupporting

confidence: 57%

Redox Induced Tunable Functionalization of Picolylamines on Selective Ru‐Platform

et al. 2020

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“…When the complexes [Ru(acac) 2 L](ClO 4 ) n (L = 3,4-dihydro-1,1′-biisoquinoline or 3,3′,4,4′-tetrahydro-1,1′-biisoquinoline, n = 0 or 1) are treated with NEt 3 under aerobic conditions, the ligands are fully aromatized and the compounds [Ru(acac) 2 (biiq)](ClO 4 ) n (n = 0 or 1) are obtained [ 140 ]. The complex rac -(Δ)-[Ru(acac) 2 {(1 M )-biiq}](ClO 4 ) has been structurally characterized (CSD Refcode OGIVEI, space group P 2/ n , Figure 12 a, N2–C1–C1′–N2′ torsion angle of 25.38°).…”

Section: Complexes Of 11′-biisoquinolinesmentioning

confidence: 99%

“…It is unclear if the change in distereoisomeric selectivity in these two compounds is a case of diastereoisomerically selective crystallization for the two crystals determined, or if it reflects a more fundamental difference in thermodynamic stability of the complexes themselves. The Ru–O and Ru–N distances in the ruthenium(II) complex (Ru–O, 2.046–2.060 Å, Ru–N, 1.991, 1.993 Å) are significantly shorter than in the ruthenium(III) compound (Ru–O, 2.010, 2.011 Å, Ru–N, 2.037 Å) [ 140 ].…”

Section: Complexes Of 11′-biisoquinolinesmentioning

confidence: 99%

1,1′-Biisoquinolines—Neglected Ligands in the Heterocyclic Diimine Family That Provoke Stereochemical Reflections

2021

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1,1′-Biisoquinolines are a class of bidentate nitrogen donor ligands in the heterocyclic diimine family. This review briefly discusses their properties and the key synthetic pathways available and then concentrates upon their coordination behaviour. The ligands are of interest as they exhibit the phenomenon of atropisomerism (hindered rotation about the C1–C1′ bond). A notation for depicting the stereochemistry in coordination compounds containing multiple stereogenic centers is developed. The consequences of the chirality within the ligand on the coordination behaviour is discussed in detail.

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Structural and Electronic Diversity as a Function of Metal Ions and Co‐ligands in Deprotonated Epindolidione Bridged Diruthenium and Diosmium Set‐up

Kumari,

Kumar Bera,

Priego

et al. 2023

Eur J Inorg Chem

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The article dealt with the structurally validated L2− (H2L=epindolidione=5,11‐dihydroquinolino[3,2‐b]quinoline‐6,12‐dione, a heteroatom‐modified tetracene and a structural isomer of indigo dye) bridged {(acac)2RuIII}2(μ‐L2−) 1/2 (S=1, acac=acetylacetonate) and [{(bpy)2OsII}2(μ‐L2−)](ClO4)2 [3](ClO4)2/[(pap)2OsII}2(μ‐L2−)](ClO4)2 [4](ClO4)2 (S=0, bpy=2,2′‐bipyridine, pap=2‐phenylazopyridine). 1/2 and [3](ClO4)2/[4](ClO4)2 with a metal‐metal separation of ≈7 Å stabilized selectively in meso(ΔΛ)/rac(ΔΔ/ΛΛ) and meso diastereomeric forms, respectively, in spite of calculated minor difference in energy between the diastereomers in each case. Though 2, [3](ClO4)2/[4](ClO4)2) exhibited intermolecular π–π interactions, no such non‐covalent interaction was perceived in 1. RuIIIRuIII derived 1/2 (S=1, 2.63/2.57 μB at 300 K) attributed to non‐interacting two Ru(III) (S=1/2) spins with an intermolecular through space weak antiferromagnetic exchange interaction below 12 K and its variable temperature 1H NMR revealed Fermi and pseudo‐contact shifts. Multiple redox steps of the complexes varied as a function of metal ion (Ru versus Os), its oxidation state (III versus II) and ancillary ligand (acac versus bpy versus pap). A collective consideration of DFT calculated MOs and Mulliken spin densities suggested delicate electronic forms along the redox chain due to the participation of bridge largely in the oxidation processes as a consequence of its redox non‐innocent feature. Reductions were however mostly centered around the metal (RuIII to RuII) and ancillary ligands (bpy/pap) in 1/2 and 32+/42+, respectively. 1n/2n, [3]2+/[4]2+ displayed mixed metal/ligand based weak low‐energy (800‐1400 nm) transitions in addition to intense visible bands as corroborated by TD‐DFT calculations.

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Non‐Spectator Feature of α‐Diimine Mimicked Di/tetrahydro‐bisisoquinoline and Biimidazopyridine on {Ru(acac)₂} Platform

Cited by 9 publications

References 85 publications

Redox Induced Tunable Functionalization of Picolylamines on Selective Ru‐Platform

Redox Induced Tunable Functionalization of Picolylamines on Selective Ru‐Platform

1,1′-Biisoquinolines—Neglected Ligands in the Heterocyclic Diimine Family That Provoke Stereochemical Reflections

Structural and Electronic Diversity as a Function of Metal Ions and Co‐ligands in Deprotonated Epindolidione Bridged Diruthenium and Diosmium Set‐up

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Non‐Spectator Feature of α‐Diimine Mimicked Di/tetrahydro‐bisisoquinoline and Biimidazopyridine on {Ru(acac)2} Platform

Cited by 9 publications

References 85 publications

Redox Induced Tunable Functionalization of Picolylamines on Selective Ru‐Platform

Redox Induced Tunable Functionalization of Picolylamines on Selective Ru‐Platform

1,1′-Biisoquinolines—Neglected Ligands in the Heterocyclic Diimine Family That Provoke Stereochemical Reflections

Structural and Electronic Diversity as a Function of Metal Ions and Co‐ligands in Deprotonated Epindolidione Bridged Diruthenium and Diosmium Set‐up

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Product

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Non‐Spectator Feature of α‐Diimine Mimicked Di/tetrahydro‐bisisoquinoline and Biimidazopyridine on {Ru(acac)₂} Platform