Solvent‐Mediated Functionalization of Benzofuroxan on Electron‐Rich Ruthenium Complex Platform

Ghosh, Prabir; Dey, Sanchaita; Panda, Sanjib; Lahiri, Goutam Kumar

doi:10.1002/asia.201800308

Cited by 14 publications

(8 citation statements)

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“…The correspondences of O1 and R1 in 1 or 2 (Figure ) to Ru(II)/Ru(III) and BTD°/BTD •– couples could be attributed to metal-based anisotropic EPR for electrochemically generated 1 + / 2 + ( S = 1/2, ⟨ g ⟩/Δ g = 2.13/0.60 and 2.12/0.57) and radical EPR response for 1 •– / 2 •– ( S = 1/2, g = 2.006/2.005), respectively , (Figure and Table ), as also corroborated by the MO compositions of 1 n and 2 n ( n = +1, 0, −1; Tables S2–S8 in the Supporting Information) and Mulliken spin density distribution at the paramagnetic ( S = 1/2) state (Figure and Table ). Chemical oxidation of 1 or 2 to 1 + or 2 + , respectively, with H 2 O 2 in CH 3 CN also resulted in an EPR response similar to that in the case of the electrochemical process (Figure S9 in the Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Ruthenium–Benzothiadiazole Building Block Derived Dynamic Heterometallic Ru–Ag Coordination Polymer and Its Enhanced Water-Splitting Feature

et al. 2021

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This article deals with the development of the unprecedented redox-mediated heterometallic coordination polymer {[Ru III (acac) 2 (μ-bis-η 1 -N,η 1 -N-BTD) 2 Ag I (ClO 4 )]ClO 4 } n (3) via the oxidation of the monomeric building block cis-[Ru II (acac) 2 (η 1 -N-BTD) 2 ] (1) by AgClO 4 (BTD = exodentate 2,1,3-benzothiadiazole, acac = acetylacetonate). Monomeric cis-[Ru II (acac) 2 (η 1 -N-BTD) 2 ] (1) and [Ru II (acac) 2 (η 1 -N-BTD)-(CH 3 CN)] (2) were simultaneously obtained from the electrondeficient BTD heterocycle and the electron-rich metal precursor Ru II (acac) 2 (CH 3 CN) 2 in refluxing CH 3 CN. Molecular identities of 1−3 were authenticated by their single-crystal X-ray structures as well as by solution spectral features. These results also reflected the elusive trigonal-planar geometry of the Ag ion in Ru−Ag-derived polymeric 3. Ru(III) (S = 1/2)-derived 3 displayed metal-based anisotropic EPR with ⟨g⟩/Δg = 2.12/0.56 and paramagnetically shifted 1 H NMR. Spectroelectrochemistry in combination with DFT/TD-DFT calculations of 1 n and 2 n (n = 1+, 0, 1−) determined a metal-based (Ru II /Ru III ) oxidation and BTD-based reduction (BTD/BTD •− ). The drastic decrease in the emission intensity and quantum yield but insignificant change in the lifetime of 3 with respect to 1 could be addressed in terms of static quenching and/or a paramagnetism-induced phenomenon. A homogeneously dispersed dumbbell-shaped morphology and the particle diameter of 3 were established by microscopic (TEM-EDX/SEM) and DLS analysis, respectively. Moreover, the dynamic nature of polymeric 3 was highlighted by its degradation to the η 1 -N-BTD coordinated monomeric fragment 1, which could also be followed spectrophotometrically in polar protic EtOH. Interestingly, both monomeric 1 and polymeric 3 exhibited efficient electrocatalytic activity toward water oxidation processes (OER, HER) on immobilization on an FTO support, which also divulged the better intrinsic water oxidation activity of 3 in comparison to 1.

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Section: Resultsmentioning

confidence: 99%

Ruthenium–Benzothiadiazole Building Block Derived Dynamic Heterometallic Ru–Ag Coordination Polymer and Its Enhanced Water-Splitting Feature

et al. 2021

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“…Conversion of earth-abundant and readily accessible small molecules such as O 2 , N 2 , H 2 , CO 2 , CH 4 , etc., into value-added chemical feedstock under mild reaction conditions has been considered to be an important event in terms of industry and the environment . However, chemical transformations of these molecules are thermodynamically demanding and mechanistically complex owing to the inertness of their bonds, and their activation poses a formidable challenge.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium-Chelated Non-Innocent Bis(heterocyclo)methanides: A Mimicked β-Diketiminate

et al. 2019

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The unexplored substrate-based reactivity profile of newly designed bis(heterocyclo)methanide (BHM, L1–L3), a structural mimic of ubiquitous β-diketiminate, was demonstrated on an electronically rich {Ru(acac)2} platform (acac = σ-donating acetylacetonate). In this regard, this work deals with structurally characterized [Ru(L)(acac)2] complexes 1A–3A incorporating electronically varying heterocycles {1A, L1 = bis(imidazo[1,5-a]pyridin-3-yl)methanide; 2A, L2 = (Z)-4-[(6,7-dihydrothieno[3,2-c]pyridin-4-yl)methylene]-6,7-dihydro-4H-thieno[3,2-c]pyridin-5-ide; 3A, L3 = (Z)-6-chloro-1-[(6-chloro-3,4-dihydroisoquinolin-1-yl)methylene]-3,4-dihydro-1H-isoquinolin-2-ide}. The significant impact of electronic modification at the BHM backbone (L1–L3) on its redox tunability at the metal–ligand interface in 1A–3A and its subsequent oxygenation profile to yield bis(heterocyclo)methanone (BMO, analogue of α-ketodiimine) in the corresponding [Ru(BMO)(acac)2] (1B–3B) via a radical pathway were rationalized. In addition, oxidative dehydrogenation of metalated BMO in 1B–3B to BAM [bis(heteroaryl)methanone] in [Ru(BAM))(acac)2] (1C–3C) was illustrated in support of the nonspectator behavior of α-ketodiimine. A combined experimental and theoretical investigation extended mechanistic outlines of the aforementioned transformation processes, which in effect provided a new dimension relating to the analogous β-diketiminate as well as α-ketodiimine chemistry.

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“…Acceleration of the reaction rate on moving from 1 to 4 in presence of NaBH 4 suggested reductive furoxan ring opening process facilitated by external stimuli. Ring fission with reduction of one of the nitroso functions of benzofuroxan in alcoholic medium was also demonstrated recently …”

Section: Resultsmentioning

confidence: 89%

Ruthenium‐Hydride Assisted Remarkable Diversity Towards Non‐Spectator Feature of Benzodifuroxan

Dey

Panda

Lahiri

2020

Chemistry An Asian Journal

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The present article demonstrates that rutheniumhydride [Ru II (H)(Cl)(CO)(PPh 3) 3 ] mediated diverse functionalization modes of benzodifuroxan (BDF) encompassing two furoxan rings. Hydride transfer from the metal precursor facilitated multiple cascade reactions involving unsymmetrical cleavage of the furoxan rings of BDF, leading to the onepot formation of a series of ruthenium (II) coordinated functionalized ligands exhibiting bidentate k 2-N,O, k 2-N,N' and bis-bidentate μ-bis(k 2-N,O) modes. Further, a moderately stable intermediate species was also encountered in the reaction sequence in which the transformed deoxygenated ligand coordinated to the metal ion via the rarely manifested furazan ring (k 2-N,N'' mode). The products were authenticated by their single-crystal X-ray structures and other spectroscopic/analytical techniques. Redox non-innocence of the functionalized ligands in the complexes was illustrated by spectroelectrochemistry (cyclic voltammmetry, UV-Vis. and EPR) in conjunction with DFT/TD-DFT calculations. Mechanistic outline for the facile ring opening processes of BDF including interconversions of complexes (e. g. reductive ring opening) were also addressed.

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Solvent‐Mediated Functionalization of Benzofuroxan on Electron‐Rich Ruthenium Complex Platform

Cited by 14 publications

References 64 publications

Ruthenium–Benzothiadiazole Building Block Derived Dynamic Heterometallic Ru–Ag Coordination Polymer and Its Enhanced Water-Splitting Feature

Ruthenium–Benzothiadiazole Building Block Derived Dynamic Heterometallic Ru–Ag Coordination Polymer and Its Enhanced Water-Splitting Feature

Ruthenium-Chelated Non-Innocent Bis(heterocyclo)methanides: A Mimicked β-Diketiminate

Ruthenium‐Hydride Assisted Remarkable Diversity Towards Non‐Spectator Feature of Benzodifuroxan

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