Diverse modes of functionalisation of ruthenium coordinated β-ketoiminate analogues

Bera, Sudip Kumar; Panda, Sanjib; Baksi, Sourajit Dey; Lahiri, Goutam Kumar

doi:10.1039/c8dt02940g

Cited by 16 publications

(14 citation statements)

References 74 publications

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“…Elongation of a newly formed C–C bond in I1 4 (>1.6 Å) and a C–O distance in I2 4 (1.493 Å) is a reflection of electronic consequence due to molecular strain . Moreover, cyclization in the presence of an acnac substituent in PA also reveals the ambiphilic feature of acnac . Finally, the greater thermodynamic stability of the products (Δ G highly negative) with respect to their metastable dianionic counterpart favors the overall transformation processes.…”

Section: Results and Discussionmentioning

confidence: 99%

Diverse Functionalization of Ruthenium-Chelated 2-Picolylamines: Oxygenation, Dehydrogenation, Cyclization, and N-Dealkylation

et al. 2020

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Chemical noninnocence" of metal-coordinated 2-picolylamine (PA) derivatives has been introduced upon its reaction with the metal precursor [Ru II (Cl)-(H)(CO)(PPh 3 ) 3 ] under basic conditions. This in effect leads to the facile formation of metalated amide, imine, ring-cyclized pyrrole, and an N-dealkylated congener based on the fine-tuning of an amine nitrogen (N amine ) and a methylene center (C α ) at the PA backbone. It develops oxygenated L1′ in 1 and cyclized L4′ in 4 upon switching of the N amine substituent of PA from aryl to an electrophilic pent-3-en-2-one moiety. On the other hand, imposing the substituent at the C α position of PA modifies its reactivity profile, leading to a dehydrogenation (2/3) or N-dealkylation (6) process. The divergent reactivity profile of metalated PA is considered to proceed through a common dianionic intermediate. Further, a competitive scenario of C−H bond functionalization of coordinated PA versus the ligand-exchange process has been exemplified in the presence of external electrophile such as benzyl bromide or methylene iodide. Authentication of the product formation as well as elucidation of the reaction pathway has been addressed by their crystal structures and spectroscopic features in conjunction with the transition-state (TS) theory.

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Section: Results and Discussionmentioning

confidence: 99%

Diverse Functionalization of Ruthenium-Chelated 2-Picolylamines: Oxygenation, Dehydrogenation, Cyclization, and N-Dealkylation

et al. 2020

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“…In this metal driven activation of substrate and oxygen, non‐innocent features of both metal and ligand have played an active role as the β‐diketiminate ligand transfers one electron to the redox active ruthenium metal and thereby the dioxygen activation takes place at the radical ligand interface. Similar contributions from the group have reiterated the leading involvement of the ligand centered radical, formed through the redox mediated canonical possibilities: Ru III ‐L – ↔ Ru II ‐L · , in giving the oxygenated product in a set of ruthenium complexes with acetylacetonate as the ancillary ligand . One particular case of interest was that of complex 11 where the rate of oxygenation was 10 fold higher with respect to the ruthenium complex with simple nacnac ligand.…”

Section: Ligand Assisted Bond Activationmentioning

confidence: 85%

Bond Activations Assisted by Redox Active Ligand Scaffolds

2020

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Redox active ligands are an integral part of many biological events and significant natural processes. Transformations assisted by such ligands gather the limelight owing to their excellent activity and selectivity towards the transformation of organic functionalities as well as activation of small molecules. The past few decades have seen an increasing demand of the field featuring its significance as the concept derived products find applications in chemical, pharmaceutical and agrochemical industries. Besides, the mechanistic insights allow for a grass root understanding of the underlining chemistry. The present article aims to highlight bond activations platformed on this concept by citing a few recent examples.

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“…The related complexes [Ru(acac) 2 (L)] (L = N,N'-disubstituted ligands) also have similar properties. [28,29] The room temperature luminescence emission spectra of complexes 1-5 (10 À 4 mol/L) in CH 2 Cl 2 solution (λ ex = 350 nm) are illustrated in Figure 2. The emission maximum for the complexes 1-5 appear at about 403 nm with weak intensity.…”

Section: Results Discussionmentioning

confidence: 99%

Photocatalytic Properties and Electronic Effects of Incorporation Bis(acetylacetonato) Ruthenium(II/III) Complexes with Bidentate Nitrogen and Sulfur Ancillaries

et al. 2021

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Treatment of cis-[Ru(acac) 2 (CH 3 CN) 2 ] (acac À = acetylacetonate) with 1.5 equiv. of corresponding bidentate nitrogen and sulfur ligands in ethanol gave a series of bis(acetylacetonato) ruthenium(II/III) complexes [(acac 4) and [(acac) 2 Ru(S 2 CNMe 2 )] (5), respectively.Complexes 1-5 were characterized by FT-IR, NMR and UV-Vis spectroscopies along with their electrochemical properties. The structures of complexes 1-5 have been unambiguously established by single crystal X-ray crystallography. The photocatalytic properties for hydrogen production by water splitting of complexes 1-5 under visible light (λ > 420 nm) were also investigated in the paper.

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Diverse modes of functionalisation of ruthenium coordinated β-ketoiminate analogues

Abstract: Varying chelation assisted as well as solvent dependent reactivity profiles of isostructural β-ketoiminate analogues explicate their non-spectator behaviour and fractional redox non-innocence.

Cited by 16 publications

References 74 publications

Diverse Functionalization of Ruthenium-Chelated 2-Picolylamines: Oxygenation, Dehydrogenation, Cyclization, and N-Dealkylation

Diverse Functionalization of Ruthenium-Chelated 2-Picolylamines: Oxygenation, Dehydrogenation, Cyclization, and N-Dealkylation

Bond Activations Assisted by Redox Active Ligand Scaffolds

Photocatalytic Properties and Electronic Effects of Incorporation Bis(acetylacetonato) Ruthenium(II/III) Complexes with Bidentate Nitrogen and Sulfur Ancillaries

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