Mixed‐Ligand Oxidovanadium(V) Complexes with <i>N′</i>‐Salicylidenehydrazides: Synthesis, Structure, and <sup>51</sup>V Solid‐State MAS NMR Investigation

Nica, Simona; Buchholz, Axel; Rudolph, Manfred; Schweitzer, Annika; Wächtler, Maria; Breitzke, Hergen; Buntkowsky, Gerd; Plass, Winfried

doi:10.1002/ejic.200800063

Cited by 35 publications

(55 citation statements)

References 49 publications

(62 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…9, 17, 23–25, 52, 53 The derived quadrupolar parameter,

C_{Q} \sqrt{1 - η^{2} / 3}

, takes into account the asymmetry parameter of the EFG tensor as well as C Q and is useful because it can be extracted based solely on the second-order quadrupolar shift. 9 Perhaps not surprisingly, there is no clear trend in these graphs that would provide a useful correlation between the NMR observables and coordination number.…”

Section: Resultsmentioning

confidence: 99%

“…2–8 The biological activity of vanadium complexes and proteins is determined by the specific chemical environment of the vanadium centers. The application of 51 V NMR to study solid vanadium-containing complexes that are of biological relevance has grown rapidly in recent years 9–25 due to the ability to acquire high quality magic angle spinning spectra of both the central and satellite NMR transitions of the 51 V (I = 7/2). Studies have demonstrated that both the quadrupolar coupling and the chemical shift anisotropy, which can be determined from the solid-state NMR spectra, are sensitive to the local vanadium environment and can be used to understand changes in the local molecular orbital structure and ground state charge distribution at the vanadium.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

51V solid-state NMR and density functional theory studies of eight-coordinate non-oxo vanadium complexes: oxidized amavadin

et al. 2009

View full text Add to dashboard Cite

SUMMARY Using 51V magic angle spinning solid-state NMR spectroscopy and Density Functional Theory calculations we have characterized the chemical shift and quadrupolar coupling parameters for two eight-coordinate vanadium complexes, [PPh4][V(V)(HIDPA)2] and [PPh4][V(V)(HIDA)2]; HIDPA = 2,2′-(hydroxyimino)dipropionate and HIDA = 2,2′-(hydroxyimino)diacetate. The coordination geometry under examination is the less common non-oxo eight coordinate distorted dodecahedral geometry that has not been previously investigated by solid-state NMR spectroscopy. Both complexes were isolated by oxidizing their reduced forms: [V(IV)(HIDPA)2]2- and [V(IV)(HIDA)2]2-. V(IV)(HIDPA)22- is also known as amavadin, a vanadium-containing natural product present in the Amanita muscaria mushroom and responsible for vanadium accumulation in nature. The quadrupolar coupling constants, CQ, are found to be moderate, 5.0 to 6.4 MHz while the chemical shift anisotropies are relatively small for vanadium complexes, −420 and 360 ppm. The isotropic chemical shifts in the solid state are −220 and −228 ppm for the two compounds, and near the chemical shifts observed in solution. Presumably this is a consequence of the combined effects of the increased coordination number and the absence of oxo groups. Density Functional Theory calculations of the electric field gradient parameters are in good agreement with the NMR results while the chemical shift parameters show some deviation from the experimental values. Future work on this unusual coordination geometry and a combined analysis by solid-state NMR and Density Functional Theory should provide a better understanding of the correlations between experimental NMR parameters and the local structure of the vanadium centers.

show abstract

“…9, 17, 23–25, 52, 53 The derived quadrupolar parameter,

C_{Q} \sqrt{1 - η^{2} / 3}

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

51V solid-state NMR and density functional theory studies of eight-coordinate non-oxo vanadium complexes: oxidized amavadin

et al. 2009

View full text Add to dashboard Cite

show abstract

“…The potentials reported in this paper refer to the ferrocenium/ferrocene couple, which has been measured at the end of each experiment (for details see ref. [38] ).…”

Section: 4-diamino-n-(4-methoxyphenyl)carbazole (1)mentioning

confidence: 93%

Copper(II) and Zinc(II) Complexes with a Photoactive Bridging Ligand Based on Carbazole: Synthesis, Structures, Electronic and Magnetic Properties

Spielberg

Plass

2011

Eur J Inorg Chem

Self Cite

View full text Add to dashboard Cite

Keywords:Copper / Zinc / EPR spectroscopy / Fluorescence / Magnetic properties / UV/Vis spectroscopy / Density functional calculationsThe synthesis of the new Schiff base ligand N-(4-methoxyphenyl)-3,4-bis(salicylidenimino)carbazole (H 2 SalCarbOMe) is described. It readily reacts with copper(II) and zinc(II) ions to form metallacycles of the general formula [M 2 (SalCarbOMe) 2 ] (M = Cu, Zn). Their structures are determined by X-ray crystallography and show significant differences for the coordination at the metal ion with a nearly tetrahedral arrangement for Zn II , but a considerable distortion towards square-planar geometry for Cu II . This in turn leads to substantial differences for the dihedral angles observed between the salicylidene and carbazole moieties. As a consequence different arrangements in the unit cell are observed, which becomes particularly obvious when the additional solvent molecules of crystallization are considered. For the Zn II compound this leads to the incorporation of a chloroform and

show abstract

“…1, 15, 33–39 A hybrid 51 V SSNMR / Density Functional Theory (DFT) approach provides highly sensitive information regarding electronic structure and geometry not only in coordination complexes 1, 15, 33–36, 41–44 but also in large proteins, such-as vanadium-containing haloperoxidases. 37 This sensitivity arises from the fact that 51 V is a half-integer quadrupolar nucleus (I=7/2).…”

Section: Introductionmentioning

confidence: 99%

Effect of ancillary ligand on electronic structure as probed by 51V solid-state NMR spectroscopy for vanadium–o-dioxolene complexes

et al. 2013

View full text Add to dashboard Cite

A series of vanadium(V) complexes with o-dioxolene (catecholato) ligands and an ancillary ligand, (N-(salicylideneaminato)ethylenediamine) (hensal), were investigated using 51V solid-state magic angle spinning NMR spectroscopy (51V MAS NMR) to assess the local environment of the vanadium(V). The solid-state 51V NMR parameters of vanadium(V) complexes with a related potentially tetradentate ancillary ligand (N-salicylidene-N′-(2-hydroxyethyl)ethylenediamine) (h2shed) were previously shown to be associated with the size of the HOMO-LUMO gap in the complex, and as such provide insights on the interaction between metal ion and ligand (P. B. Chatterjee, et al., Inorg. Chem 50 (2011) 9794). Our results show that the modification of the ancillary ligand does not impact the observed trend between complexes ranging from catechols with electron rich to electron poor substituents. However, the ancillary ligand does impact the size of the HOMO-LUMO separation in the parent complex and thus the solid-state vanadium NMR chemical shift of the unsubstituted vanadium complex. For these complexes significant changes observed in the isotropic shifts and more modest changes detected in the CQ reflect the electronic changes in the complex as the catechol is varied. However, no obvious trend was observed in the chemical shift anisotropies (δσ and ησ) with the variation in the catechol. The electronic changes in the coordination environment of the vanadium can be described using solid-state 51V NMR spectroscopy.

show abstract

Mixed‐Ligand Oxidovanadium(V) Complexes with N′‐Salicylidenehydrazides: Synthesis, Structure, and ⁵¹V Solid‐State MAS NMR Investigation

Cited by 35 publications

References 49 publications

51V solid-state NMR and density functional theory studies of eight-coordinate non-oxo vanadium complexes: oxidized amavadin

51V solid-state NMR and density functional theory studies of eight-coordinate non-oxo vanadium complexes: oxidized amavadin

Copper(II) and Zinc(II) Complexes with a Photoactive Bridging Ligand Based on Carbazole: Synthesis, Structures, Electronic and Magnetic Properties

Effect of ancillary ligand on electronic structure as probed by 51V solid-state NMR spectroscopy for vanadium–o-dioxolene complexes

Contact Info

Product

Resources

About

Mixed‐Ligand Oxidovanadium(V) Complexes with N′‐Salicylidenehydrazides: Synthesis, Structure, and 51V Solid‐State MAS NMR Investigation

Cited by 35 publications

References 49 publications

51V solid-state NMR and density functional theory studies of eight-coordinate non-oxo vanadium complexes: oxidized amavadin

51V solid-state NMR and density functional theory studies of eight-coordinate non-oxo vanadium complexes: oxidized amavadin

Copper(II) and Zinc(II) Complexes with a Photoactive Bridging Ligand Based on Carbazole: Synthesis, Structures, Electronic and Magnetic Properties

Effect of ancillary ligand on electronic structure as probed by 51V solid-state NMR spectroscopy for vanadium–o-dioxolene complexes

Contact Info

Product

Resources

About

Mixed‐Ligand Oxidovanadium(V) Complexes with N′‐Salicylidenehydrazides: Synthesis, Structure, and ⁵¹V Solid‐State MAS NMR Investigation