First example of a 1:1 vanadium(IV)–citrate complex featuring the 2,2′-bipyridine co-ligand: Synthesis, X-ray crystal structure and DFT calculations

Jodaian, Vida; Mirzaei, Masoud; Arca, Massimiliano; Aragoni, M. Carla; Lippolis, Vito; Tavakoli, Elnaz; Langeroodi, Narges Samadani

doi:10.1016/j.ica.2013.02.012

Cited by 13 publications

(11 citation statements)

References 51 publications

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“…IR (KBr, cm −1 ): ν as (CO 2 H), 1720 m ; ν as (CO 2 ), 1604 vs ; ν s (CO 2 ), 1446 m , 1386 s , 1346 m ; ν (V=O), 988 m , 952 m . The data are similar to that of [VO(H 2 cit)(bpy)]·1.5H 2 O [33]…”

Section: Methodssupporting

confidence: 78%

“…Unlike the reaction of vanadium(III) chloride with bipyridine and citric acid [33], direct reaction of vanadyl sulfate with excess H 3 mal, H 4 cit or S -H 3 citmal is delicately sensitive to pH adjustment, as demonstrated by a digital pH monitor. The reaction takes place in the presence of bpy or phen in an aqueous ethanol solution.…”

Section: Resultsmentioning

confidence: 99%

“…In the previous study of vanadium hydroxypolycarboxylate complexes, most of the investigations have addressed the coordination chemistry of citrate vanadates [17–25] and vanadyl complexes [25–31]. The mixed-ligand complexes have been reported as dimers [V 2 O 3 (phen) 3 (Hcit)]·5H 2 O, [V 2 O 3 (phen) 3 (Hcit) 2 (phen) 3 O 3 V 2 ]·12H 2 O [32] and monomer [VO(H 2 cit)(bpy)]·1.5H 2 O [33] (H 4 cit = citric acid, phen = 1,10–phenanthroline, and bpy = 2,2′–bipyridine). The formers are coordinated by citrate with α-alkoxy group, while the later is coordinated by citrate with α-hydroxy group.…”

Section: Introductionmentioning

confidence: 99%

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α-Hydroxy coordination of mononuclear vanadyl citrate, malate and S-citramalate with N-heterocycle ligand, implying a new protonation pathway of iron–vanadium cofactor in nitrogenase

Chen

et al. 2014

Journal of Inorganic Biochemistry

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Unlike the most of α-alkoxy coordination in α-hydroxycarboxylates to vanadium, novel α-hydroxy coordination to vanadium(IV) has been observed for a series of chiral and achiral monomeric α-hydroxycarboxylato vanadyl complexes [VO(H2cit)(bpy)]·2H2O (1), [VO(Hmal)(bpy)]·H2O (2), [VO(H2cit)(phen)]·1.5H2O (3), [VO(Hmal)(phen)]·H2O (4), and [ΔVO(S-Hcitmal)(bpy)]·2H2O (5), [VO(H2cit)(phen)]2·6.5H2O (6), which were isolated from the reactions of vanadyl sulfate with α-hydroxycarboxylates and N-heterocycle ligands in acidic solution. The complexes feature a tridentate citrate, malate or citramalate that chelates to vanadium atom through their α–hydroxy, α–carboxy and β–carboxy groups; while the other β–carboxylic acidic group of citrate is free to participate strong hydrogen bonds with lattice water molecule. The neutral α-hydroxy group also forms strong intermolecular hydrogen bonds with water molecule and the negatively-charged α-carboxy group in the environment. The inclusion of a hydrogen ion in α–alkoxy group results in the formation of a series of neutral complexes with one less positive charge. There are two different configurations of citrate with respect to the trans-position of axial oxo group, where the complex with trans-hydroxy configuration seems more stable with less hindrance. The average bond distances of V–Ohydroxy and V–Oα-carboxy are 2.196 and 2.003 Å respectively, which are comparable to the V–O distance (2.15 Å) of homocitrate in FeV–cofactor of V–nitrogenase. A new structural model is suggested for R-homocitrato iron vanadium cofactor as VFe7S9C(R-Hhomocit) (H4homocit = homocitric acid) with one more proton in homocitrate ligand.

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Section: Methodssupporting

confidence: 78%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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α-Hydroxy coordination of mononuclear vanadyl citrate, malate and S-citramalate with N-heterocycle ligand, implying a new protonation pathway of iron–vanadium cofactor in nitrogenase

Chen

et al. 2014

Journal of Inorganic Biochemistry

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“…These α-hydroxycarboxylates bind to the vanadium atom through their α-alkoxy, α-carboxy and/or β-carboxy groups. Vanadium α-hydroxycarboxylates with unusual α-hydroxy coordination are also reported [29,32]. These crystalline compounds have dimeric cores or mononuclear forms.…”

Section: Introductionmentioning

confidence: 97%

Degradations of novel tetranuclear vanadyl glycollates to dinuclear species

Jin

Zhou

2017

Polyhedron

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Novel tetranuclear vanadyl glycollates [Ni(phen) 3 ] 2 [V IV 4 O 4 (glyc) 6 ]•23H 2 O (1) and [Ni(phen) 3 ] 2 [V IV 4 O 4 (glyc) 6 ]•16H 2 O (2) have been obtained through the capture of bulky nickel phenanthroline cation (H 2 glyc = glycollic acid, phen =1,10-phenanthroline), and the mixed-ligand complex [V IV 4 O 6 (glyc) 2 (bpy) 4 ]•6H 2 O (3) (bpy = 2,2'-bipyridine) was isolated with the addition of bpy under hydrothermal condition. Tetrameric 1 and 2 are easily oxidized to dimeric complex [Ni(phen) 3 ][V V 2 O 4 (glyc) 2 ]•5H 2 O (4), while 3 with bipyridine is stable. The degradation process was traced by IR and XRD experiment. 1 ~ 4 feature bidentate glycollate that chelates to vanadium atom through α-alkoxy and α-carboxy groups, which were full characterized by elemental analysis, TG, IR, UV-vis, EPR, XRD and X-ray structural analyses. Bond valence calculation is also performed.

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“…In particular, the pyridine-2,6-dicarboxylic acid (hereafter denoted as H 2 pydc) by variable coordination modes can produce new coordination complexes with different metals and also proton transfer salts with diverse organic bases [18]. Recent studies show that the complexes of the vanadium [19,20] and cobalt [21] with H 2 pydc are effective in normalizing blood glucose level in diabetics or it can be used as a decontamination agent in nuclear reactors by chelating with heavy metals like uranium [22]. In many articles, it is also referred to as a germicidal agent in water [16,17].…”

Section: Introductionmentioning

confidence: 99%

Syntheses and X-ray crystal structure studies of four new coordination complexes and salts based on proton-transferred pyridine-2,6-dicarboxylic acid N-oxide

2015

Self Cite

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Four new supramolecular coordination complexes and salts based on proton-transferred pyridine-2,6-dicarboxylic acid N-oxide formulated as (Htata) (Hpydco)ÁH 2 O (1), (Htata) 2 (pydco)Á2H 2 O (2), (H9a-acr) 2 [Zn(pydco) 2 (H 2 O) 2 ]Á4H 2 O (3), and (H9a-acr) 2 [Co(pydco) 2 (H 2 O) 2 ]Á4H 2 O (4) (where H 2 pydco = pyridine-2,6-dicarboxylic acid N-oxide, tata = 2,4,6-triamino-1,3,5-triazine (melamine) and 9a-acr = 9-aminoacridine) have been synthesized by proton transfer from H 2 pydco as ligand and to tata and 9a-acr. The structures of 1-4 were characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray diffraction methods. Compounds 1 and 2 are salts of proton-transferred H 2 pydco and melamine with two separate formulas. There is a difference between the anionic fragment in 1 and 2, the anionic part of 1 retains one acid proton (Hpydco -) which is involved in a strong, intramolecular hydrogen bonding with the oxygen attached to nitrogen, while the acid units in 2 are fully deprotonated (pydco 2-). The linear chains of melaminium cations with an anionic motif and water molecules lead to 2-D zipper layers in 1 and 2-D zigzag layers in 2. These layers are held together via an extensive network of hydrogen bonds, p ? -p 1 stacking, N ? -H_p ? , and lp_p ? interactions to extend the structures into the 3-D supramolecular framework. Single-crystal studies revealed that 3 and 4 are isostructural with distorted octahedral geometry about the metal consisting of two pydco 2-ligands acting in bidentate fashion and two transdisposed water molecules. They also adopt alternating cationic and anionic layers with 9-aminoacridinium cations and transition metal complex anions which are linked to each other by a variety of noncovalent interactions such as ion pairing, hydrogen bonding and p-p stacking.

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First example of a 1:1 vanadium(IV)–citrate complex featuring the 2,2′-bipyridine co-ligand: Synthesis, X-ray crystal structure and DFT calculations

Cited by 13 publications

References 51 publications

α-Hydroxy coordination of mononuclear vanadyl citrate, malate and S-citramalate with N-heterocycle ligand, implying a new protonation pathway of iron–vanadium cofactor in nitrogenase

α-Hydroxy coordination of mononuclear vanadyl citrate, malate and S-citramalate with N-heterocycle ligand, implying a new protonation pathway of iron–vanadium cofactor in nitrogenase

Degradations of novel tetranuclear vanadyl glycollates to dinuclear species

Syntheses and X-ray crystal structure studies of four new coordination complexes and salts based on proton-transferred pyridine-2,6-dicarboxylic acid N-oxide

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