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Mixed-ligand oxidovanadium(V) complexes with N '-salicylidenehydrazides: Synthesis, structure, and V-51 solid-state MAS NMR investigation

Nica, S. and Buchholz, A. and Rudolph, M. and Schweitzer, A. and Waechtler, M. and Breitzke, H. and Buntkowsky, G. and Plass, W. (2008):
Mixed-ligand oxidovanadium(V) complexes with N '-salicylidenehydrazides: Synthesis, structure, and V-51 solid-state MAS NMR investigation.
In: European Journal of Inorganic Chemistry, (14), pp. 2350-2359, [Online-Edition: http://apps.webofknowledge.com/full_record.do?product=WOS&se...],
[Article]

Abstract

The synthesis and spectroscopic characterization of a series of three oxidovanadium(V) complexes with 8-hydroxyquinoline and Schiff-base ligdnds derived from salicylaldehyde and omega-hydroxy-functionalized carbohydrazides with different chain lengths are reported. The complex with the hydrazone ligand containing the shortest chain length was crystallographically characterized. This complex crystallizes in the triclinic space group Pi with two structurally similar but crystallographically independent oxidovanadium(V) complexes. Each vanadium atom is six-coordinate in a distorted-octahedral geometry. The two molecules are assembled through hydrogen-bonding interactions between the hydroxyl groups of the side-chain substituted Schiff-base ligand and the oxido group of one of the two complexes. Electrochemical measurements performed in acetonitrile solution reveal two reversible one-electron reduction steps. The observed pre-wave feature of the second reduction step indicates the presence of dissociation equilibria related to the 8-hydroxyquinoline coligand. Magic-angle spinning solidstate V-51 NMR spectroscopy allowed to characterize the full series of complexes with alkyl and hydroxy alkyl-substituted hydrazone ligands that were used. The quadrupolar coupling constants are small with a value of about 4 MHz and show little variation within the series. The asymmetry of the chemical shift tensor indicates a rather axial symmetric environment around the vanadium(V) center. The isotropic chemical shifts observed in the solid state occur at about 30 ppm, which is in the same order of magnitude as the solvent induced variations, about 10 ppm, found for different solvents. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

Item Type: Article
Erschienen: 2008
Creators: Nica, S. and Buchholz, A. and Rudolph, M. and Schweitzer, A. and Waechtler, M. and Breitzke, H. and Buntkowsky, G. and Plass, W.
Title: Mixed-ligand oxidovanadium(V) complexes with N '-salicylidenehydrazides: Synthesis, structure, and V-51 solid-state MAS NMR investigation
Language: English
Abstract:

The synthesis and spectroscopic characterization of a series of three oxidovanadium(V) complexes with 8-hydroxyquinoline and Schiff-base ligdnds derived from salicylaldehyde and omega-hydroxy-functionalized carbohydrazides with different chain lengths are reported. The complex with the hydrazone ligand containing the shortest chain length was crystallographically characterized. This complex crystallizes in the triclinic space group Pi with two structurally similar but crystallographically independent oxidovanadium(V) complexes. Each vanadium atom is six-coordinate in a distorted-octahedral geometry. The two molecules are assembled through hydrogen-bonding interactions between the hydroxyl groups of the side-chain substituted Schiff-base ligand and the oxido group of one of the two complexes. Electrochemical measurements performed in acetonitrile solution reveal two reversible one-electron reduction steps. The observed pre-wave feature of the second reduction step indicates the presence of dissociation equilibria related to the 8-hydroxyquinoline coligand. Magic-angle spinning solidstate V-51 NMR spectroscopy allowed to characterize the full series of complexes with alkyl and hydroxy alkyl-substituted hydrazone ligands that were used. The quadrupolar coupling constants are small with a value of about 4 MHz and show little variation within the series. The asymmetry of the chemical shift tensor indicates a rather axial symmetric environment around the vanadium(V) center. The isotropic chemical shifts observed in the solid state occur at about 30 ppm, which is in the same order of magnitude as the solvent induced variations, about 10 ppm, found for different solvents. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

Journal or Publication Title: European Journal of Inorganic Chemistry
Number: 14
Uncontrolled Keywords: 8-hydroxyquinoline schiff bases square-wave voltarnmetry vanadium v-51 nmr spectroscopy modeling supramolecular interactions nuclear-magnetic-resonance vanadium-dependent haloperoxidases density-functional theory dioxovanadium(v) complexes oxovanadium(v) complexes hydrogen-peroxide crystal-structure active-site spectroscopy
Divisions: 07 Department of Chemistry
07 Department of Chemistry > Physical Chemistry
Date Deposited: 27 Oct 2014 20:47
Official URL: http://apps.webofknowledge.com/full_record.do?product=WOS&se...
Additional Information:

306FH Times Cited:24 Cited References Count:50

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