Evolution of metal-thiocarboxylate chemistry in 21st century

Singh, Suryabhan

doi:10.1016/j.molstruc.2021.130184

Cited by 4 publications

(7 citation statements)

References 133 publications

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“…The assignment of the two methylene protons at δ H 3.23 and 3.79 at C-16 (DMSO-d 6 , 400 MHz, 348.15 K, Figure S10B) was confirmed by the correlation between those protons observed in 1 1).…”

Section: ■ Results and Discussionmentioning

confidence: 63%

“…These chemical shift assignments were supported by DFT calculations. 1 H NMR line shape analysis of the signal at position C-18 of the Ga(III)-photoxenobactin E complex (2) estimated the temperature of coalescence in DMSO-d 6 at 313.15 K. Using WinDNMR software and the Eyring equation, the kinetic parameters for the PxbE-Ga(III) tautomer were calculated. To the best of our knowledge, carbon NMR chemical resonances associated with the Ga(III)bound thione-form have not been described in the literature.…”

Section: ■ Conclusionmentioning

confidence: 99%

“…1 H and13 C NMR Data of apo-Photoxenobactin E (1, Reported by Bode and Co-Workers25 ) and for Ga(III)-Photoxenobactin E Tautomers (2A/B) at 298.15 K (Slow Exchange) and at 348.15 K (2T) (Fast Exchange) in DMSO-d 6 assigned by1 H, 1 H−COSY and 1 H,13 C-HSQC NMR experiments, hence quaternary carbons are not listed.…”

mentioning

confidence: 99%

“…1 H and13 C NMR Data Assignments of the Ga(III)-Photoxenobactin E Tautomers (2A/B) in DMSO-d 6 , CDCl 3 , and THF-d 8 (500/125 MHz, 298.15 K) a exchange process by running the NMR spectra in different deuterated solvents (Tables1 and 2; Figures S12− S19) 44. Although the best solubility was obtained in DMSO-d 6 and in a DMSO-d 6 :CD 3 OD (9:1) mixture, the Ga(III)photoxenobactin E complex (2) was also soluble in CDCl3 and partially soluble in THF-d 8 , but it was insoluble in CD 3 OD and D 2 O.…”

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confidence: 99%

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O-versus S-Metal Coordination of the Thiocarboxylate Group: An NMR Study of the Two Tautomeric Forms of the Ga(III)-Photoxenobactin E Complex

Buedenbender,

Ageitos,

Lages

et al. 2024

Inorg. Chem.

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Photoxenobactin E ( 1) is a natural product with an unusual thiocarboxylic acid terminus recently isolated from an entomopathogenic bacterium. The biosynthetic gene cluster associated with photoxenobactin E, and other reported derivatives, is very similar to that of piscibactin, the siderophore responsible for the iron uptake among bacteria of the Vibrionaceae family, including potential human pathogens. Here, the reisolation of 1 from the fish pathogen Vibrio anguillarum RV22 cultured under iron deprivation, its ability to chelate Ga(III), and the full NMR spectroscopic characterization of the Ga(III)-photoxenobactin E complex are presented. Our results show that Ga(III)-photoxenobactin E in solution exists in a thiol−thione tautomeric equilibrium, where Ga(III) is coordinated through the sulfur (thiol form) or oxygen (thione form) atoms of the thiocarboxylate group. This report represents the first NMR study of the chemical exchange between the thiol and thione forms associated with thiocarboxylate-Ga(III) coordination, including the kinetics of the interconversion process associated with this tautomeric exchange. These findings show significant implications for ligand design as they illustrate the potential of the thiocarboxylate group as a versatile donor for hard metal ions such as Ga(III).

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Section: ■ Results and Discussionmentioning

confidence: 63%

Section: ■ Conclusionmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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O-versus S-Metal Coordination of the Thiocarboxylate Group: An NMR Study of the Two Tautomeric Forms of the Ga(III)-Photoxenobactin E Complex

Buedenbender,

Ageitos,

Lages

et al. 2024

Inorg. Chem.

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“…For the synthesis of the ligand, fCOS − , a method similar to that reported for thiobenzoic acid was followed. 18 To a solution of KSH (15.60 g, 0.0278 moles) in ethanol (80 mL), 2-furoyl chloride (18.14 g, 13.7 mL, and 0.139 moles) was added drop-wise with stirring for 1 h in an ice bath. The reaction mixture was further stirred for 1 h and then filtered off the precipitate of KCl.…”

Section: N Nmentioning

confidence: 99%

On-Site H₂O₂ Synthesis Using a Series of Ni(II) Furan-2-thiocarboxylate Complexes Integrated on Multi-Walled Carbon Nanotubes: Soft Donor Sites Stimulated Selective Two-Electron Oxygen Reduction

Kumar

Singh

Adak

et al. 2023

Crystal Growth & Design

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A series of Ni(II) complexes [Ni(tmeda)(fCOS) 2 ] (1a), [Ni(2,2′-bipy)(fCOS) 2 ] (1b), [Ni(1,10-Phen)(fCOS) 2 ] (1c), [Ni(opda) 2 (fCOS) 2 ] (2), [Ni(dppe)(fCOS) 2 ] (3a), and [Ni(dppee)(fCOS) 2 ] (3b) (fCOS = furan-2-thiocarboxylate) have been synthesized. All the complexes, except 1b, were characterized by single-crystal X-ray diffraction analysis and spectroscopic techniques. In the solid state, the geometry around the Ni(II) center is square planar in the cases of 3a and 3b, while the same is octahedral (with varying degrees of distortion) in all other complexes. The complexes were integrated separately on multi-walled carbon nanotubes (MWCNTs) to prepare their respective composites. Electrochemical characteristics and oxygen reduction response of all the composites were studied. All composites exhibited a two-electron oxygen reduction process. The composite of complex 2 (2@MWCNTs) having S and N donor sites shows the highest onset potential and the highest rate of oxygen reduction. Composites of complexes having P and S coordination sites (3a@MWCNTs and 3b@MWCNTs) show relatively high selectivity toward the two-electron oxygen reduction. The composites of complexes having S, N, and O coordination sites (1a@MWCNTs, 1b@MWCNTs, and 1c@MWCNTs) show moderate selectivity and activity for the two-electron oxygen reduction. 3a@MWCNTs show the optimum combination of activity and selectivity for H 2 O 2 production. Remarkably, all the composites show high durability and may be suitable for the long-term oxygen-reduction process to synthesize H 2 O 2 .

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Synthesis and characterization of mono- and bi-iron chalcogeno-ferrocenylcarboxylato complexes

El-khateeb,

Al-Momani,

Garcia-Orduna

et al. 2024

Journal of Molecular Structure

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Evolution of metal-thiocarboxylate chemistry in 21st century

Cited by 4 publications

References 133 publications

O-versus S-Metal Coordination of the Thiocarboxylate Group: An NMR Study of the Two Tautomeric Forms of the Ga(III)-Photoxenobactin E Complex

O-versus S-Metal Coordination of the Thiocarboxylate Group: An NMR Study of the Two Tautomeric Forms of the Ga(III)-Photoxenobactin E Complex

On-Site H₂O₂ Synthesis Using a Series of Ni(II) Furan-2-thiocarboxylate Complexes Integrated on Multi-Walled Carbon Nanotubes: Soft Donor Sites Stimulated Selective Two-Electron Oxygen Reduction

Synthesis and characterization of mono- and bi-iron chalcogeno-ferrocenylcarboxylato complexes

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Evolution of metal-thiocarboxylate chemistry in 21st century

Cited by 4 publications

References 133 publications

O-versus S-Metal Coordination of the Thiocarboxylate Group: An NMR Study of the Two Tautomeric Forms of the Ga(III)-Photoxenobactin E Complex

O-versus S-Metal Coordination of the Thiocarboxylate Group: An NMR Study of the Two Tautomeric Forms of the Ga(III)-Photoxenobactin E Complex

On-Site H2O2 Synthesis Using a Series of Ni(II) Furan-2-thiocarboxylate Complexes Integrated on Multi-Walled Carbon Nanotubes: Soft Donor Sites Stimulated Selective Two-Electron Oxygen Reduction

Synthesis and characterization of mono- and bi-iron chalcogeno-ferrocenylcarboxylato complexes

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On-Site H₂O₂ Synthesis Using a Series of Ni(II) Furan-2-thiocarboxylate Complexes Integrated on Multi-Walled Carbon Nanotubes: Soft Donor Sites Stimulated Selective Two-Electron Oxygen Reduction