Spectroscopic differences between heterocyclic benzothiazoline, -thiazole and imine containing ligands and comparison of the Co and Cu pyridine benzothiazole and imine complexes

Carlson, Luke; Welby, Jenna; Zebrowski, Kelly A.; Wilk, Matthew M.; Giroux, Rachel; Ciancio, Nicole; Tanski, Joseph M.; Bradley, Amy L.; Tyler, Laurie A.

doi:10.1016/j.ica.2010.09.002

Cited by 26 publications

(13 citation statements)

References 34 publications

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“…2-(Pyridin-2-yl)benzo[ d ]thiazole ( L1 ), 2-(4-( tert -butyl)pyridin-2-yl)benzo[ d ]thiazole ( L2 ), and 2-(pyridin-2-yl)benzo[ d ]oxazole ( L6 ) were prepared by adaptation of a copper-catalyzed coupling reaction described in the literature . 2,6-Bis(benzo[ d ]thiazol-2-yl)pyridine ( L5 ) and 2,2′-bibenzo[ d ]thiazole ( L7 ) were synthesized following reported literature procedures by a condensation reaction of 2-aminothiophenol with 2,6-pyridinedicarboxaldehyde or oxalic acid, respectively. The synthesis of 2-(6-phenylpyridin-2-yl)benzo[ d ]thiazole ( L3 ) and 2-(4-( tert -butyl)-6-phenylpyridin-2-yl)benzo[ d ]thiazole ( L4 ) has not yet been reported.…”

Section: Resultsmentioning

confidence: 99%

Highly Stable Red-Light-Emitting Electrochemical Cells

et al. 2017

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The synthesis and characterization of a series of new cyclometalated iridium(III) complexes [Ir(ppy)(NN)][PF] in which Hppy = 2-phenylpyridine and NN is (pyridin-2-yl)benzo[d]thiazole (L1), 2-(4-(tert-butyl)pyridin-2-yl)benzo[d]thiazole (L2), 2-(6-phenylpyridin-2-yl)benzo[d]thiazole (L3), 2-(4-(tert-butyl)-6-phenylpyridin-2-yl)benzo[d]thiazole (L4), 2,6-bis(benzo[d]thiazol-2-yl)pyridine (L5), 2-(pyridin-2-yl)benzo[d]oxazole (L6), or 2,2'-dibenzo[d]thiazole (L7) are reported. The single crystal structures of [Ir(ppy)(L1)][PF]·1.5CHCl, [Ir(ppy)(L6)][PF]·CHCl, and [Ir(ppy)(L7)][PF] have been determined. The new complexes are efficient red emitters and have been used in the active layers in light-emitting electrochemical cells (LECs). The effects of modifications of the 2-(pyridin-2-yl)benzo[d]thiazole ligand on the photoluminescence and LEC performance have been examined. Extremely stable red-emitting LECs are obtained, and when [Ir(ppy)(L1)][PF], [Ir(ppy)(L2)][PF], or [Ir(ppy)(L3)][PF] are used in the active layer, device lifetimes greater than 1000, 6000, and 4000 h, respectively, are observed.

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Section: Resultsmentioning

confidence: 99%

Highly Stable Red-Light-Emitting Electrochemical Cells

et al. 2017

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“…The non-bulky ligands were derived from condensation of the substituted pyridine carboxaldehyde or ketone with 2-aminobenzenethiol, based on the literature report (Scheme ). , The thermodynamically more favorable benzothiazoline products were obtained as a result of cyclization after condensation (Scheme ), wherein the benzothiazoline features an S/N heterocyclic five-membered ring that can be easily opened by metal ions or organic bases . The formation of the benzothiazoline was demonstrated by NMR and IR spectroscopies as follows.…”

Section: Resultsmentioning

confidence: 99%

Effects of Thiolate Ligation in Monoiron Hydrogenase (Hmd): Stability of the {Fe(CO)₂}²⁺ Core with NNS Ligands

et al. 2018

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In this work, we report the effects of NNS-thiolate ligands and nuclearity (monomer, dimer) on the stability of iron complexes related to the active site of monoiron hydrogenase (Hmd). A thermally stable iron(II) dicarbonyl motif is the core feature of the active site, but the coordination features that lead to this property have not been independently evaluated for their contributions to the {Fe(CO)} stability. As such, non-bulky and bulky benzothiazoline ligands (thiolate precursors) were synthesized and their iron(II) complexes characterized. The use of non-bulky thiolate ligands and low-temperature crystallizations result in isolation of the dimeric species [(NNS)Fe(CO)(I)] (1), [(NNS)Fe(CO)(I)] (2), and [(NNS)Fe(CO)(I)] (3), which exhibit dimerization via thiolato (μ-S) bridges. In one particular case (unsubstituted NNS ligand), the pathway of decarbonylation and oxidation from 1 was crystallographically elucidated, via isolation of the half-bis-ligated monocarbonyl dimer [(NNS)Fe(CO)]I (4) and the fully decarbonylated and oxidized mononuclear [(NNS)Fe]I (5). The transformations of dicarbonyl complexes (1, 2, and 3) to monocarbonyl complexes (4, 6, and 7) were monitored by UV/vis, demonstrating that 1 and 3 exhibit longer t (80 and 75 min, respectively) than 2 (30 min), which is attributed to distortion of the ligand backbone. Density functional theory calculations of isolated complexes and putative intermediates were used to corroborate the experimentally observed IR spectra. Finally, dimerization was prevented using a bulky ligand featuring a 2,6-dimethylphenyl substituent, which affords mononuclear iron dicarbonyl complex, [(NNS)Fe(CO)Br] (8), identified by IR and NMR spectroscopies. The dicarbonyl complex decomposes to the decarbonylated [(NNS)Fe] (9) within minutes at room temperature. Overall, the work herein demonstrates that the thiolate moiety does not impart thermal stability to the {Fe(CO)} unit formed in the active site, further indicating the importance of the organometallic Fe-C(acyl) bond in the enzyme.

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“…Themass and 1 HNMR spectra of the isolated solid (Figure S27), however,r evealed that HL Bzn !L Bz oxidation may occur as reported. [31] Themost probable pathway of 2! {3 + L BznÀ }transformation is shown in Scheme 5.…”

Section: Angewandte Chemiementioning

confidence: 99%

Nickel(II)‐Mediated Reversible Thiolate/Disulfide Conversion as a Mimic for a Key Step of the Catalytic Cycle of Methyl‐Coenzyme M Reductase

et al. 2020

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According to the well‐accepted mechanism, methyl‐coenzyme M reductase (MCR) involves Ni‐mediated thiolate‐to‐disulfide conversion that sustains its catalytic cycle of methane formation in the energy saving pathways of methanotrophic microbes. Model complexes that illustrate Ni‐ion mediated reversible thiolate/disulfide transformation are unknown. In this paper we report the synthesis, crystal structure, spectroscopic properties and redox interconversions of a set of NiII complexes comprising a tridentate N2S donor thiol and its analogous N4S2 donor disulfide ligands. These complexes demonstrate reversible NiII‐thiolate/NiII‐disulfide (both bound and unbound disulfide‐S to NiII) transformations via thiyl and disulfide monoradical anions that resemble a primary step of MCR's catalytic cycle.

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Spectroscopic differences between heterocyclic benzothiazoline, -thiazole and imine containing ligands and comparison of the Co and Cu pyridine benzothiazole and imine complexes

Cited by 26 publications

References 34 publications

Highly Stable Red-Light-Emitting Electrochemical Cells

Highly Stable Red-Light-Emitting Electrochemical Cells

Effects of Thiolate Ligation in Monoiron Hydrogenase (Hmd): Stability of the {Fe(CO)₂}²⁺ Core with NNS Ligands

Nickel(II)‐Mediated Reversible Thiolate/Disulfide Conversion as a Mimic for a Key Step of the Catalytic Cycle of Methyl‐Coenzyme M Reductase

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Spectroscopic differences between heterocyclic benzothiazoline, -thiazole and imine containing ligands and comparison of the Co and Cu pyridine benzothiazole and imine complexes

Cited by 26 publications

References 34 publications

Highly Stable Red-Light-Emitting Electrochemical Cells

Highly Stable Red-Light-Emitting Electrochemical Cells

Effects of Thiolate Ligation in Monoiron Hydrogenase (Hmd): Stability of the {Fe(CO)2}2+ Core with NNS Ligands

Nickel(II)‐Mediated Reversible Thiolate/Disulfide Conversion as a Mimic for a Key Step of the Catalytic Cycle of Methyl‐Coenzyme M Reductase

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Effects of Thiolate Ligation in Monoiron Hydrogenase (Hmd): Stability of the {Fe(CO)₂}²⁺ Core with NNS Ligands