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• W2912194529 endingPage "2532" @default.
• W2912194529 startingPage "2523" @default.
• W2912194529 abstract "A similar pair of protonated and deprotonated mononuclear oxidovanadium glycolates [VO(Hglyc)(phen)(H2O)]Cl·2H2O (1) and [VO(glyc)(bpy)(H2O)] (2) and a mixed-(de)protonated oxidovanadium triglycolate (NH4)2[VO(Hglyc)2(glyc)]·H2O (3) were isolated and examined. The ≡C–O(H) (≡C–OH or ≡C–O) groups coordinated to vanadium were spectroscopically and structurally identified. The glycolate in 1 features a bidentate chelation through protonated α-hydroxy and α-carboxy groups, whereas the glycolate in 2 coordinates through deprotonated α-alkoxy and α-carboxy groups. The glycolates in 3 coordinate to vanadium through α-alkoxy or α-hydroxy and α-carboxy groups and thus have both protonated ≡C–OH and deprotonated ≡C–O bonds simultaneously. Structural investigations revealed that the longer protonated V–Oα-hydroxy bonds [2.234(2) Å and 2.244(2) Å] in 1 and 3 are close to those of FeV-cofactor (FeV-co) 2.17 Å1 (FeMo-co 2.17 Å2), while deprotonated V–Oα-alkoxy bonds [2, 1.930(2); 3, 1.927(2) Å] were obviously shorter. This shows a similar elongated trend as the Mo–O distances in the previously reported deprotonated vs protonated molybdenum lactates (Wang, S. Y. et al. Dalton Trans. 2018, 47, 7412–7421) and these vanadium and molybdenum complexes have the same local V/Mo-homocitrate structures as those of FeV/Mo-cos of nitrogenases. The IR spectra of these oxidovanadium and the previously synthesized molybdenum complexes including different substituted ≡C–O(H) model compounds show red-shifts for ≡C–OH vs ≡C–O alternation, which further assign the two IR bands of extracted FeMo-co at 1084 and 1031 cm–1 to ≡C–O and ≡C–OH vibrations, respectively. Although the structural data or IR spectra for some of the previously synthesized Mo/V complexes and extracted FeMo-co were measured earlier, this is the first time that the ≡C–O(H) coordinated peaks are assigned. The overall structural and IR results well suggest the coexistence of homocitrates coordinated with α-alkoxy (deprotonated) and α-hydroxy (protonated) groups in the extracted FeMo-co." @default.
• W2912194529 created "2019-02-21" @default.
• W2912194529 creator A5011735129 @default.
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• W2912194529 creator A5028889294 @default.
• W2912194529 creator A5039876008 @default.
• W2912194529 creator A5047766796 @default.
• W2912194529 creator A5060461431 @default.
• W2912194529 creator A5075969066 @default.
• W2912194529 date "2019-02-06" @default.
• W2912194529 modified "2023-10-17" @default.
• W2912194529 title "Preliminary Assignment of Protonated and Deprotonated Homocitrates in Extracted FeMo-Cofactors by Comparisons with Molybdenum(IV) Lactates and Oxidovanadium Glycolates" @default.
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