English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  Nonoxovanadium(IV) and Oxovanadium(V) Complexes with Mixed O, X, O-Donor Ligands (X = S, Se, P, or PO)

Paine, T. K., Weyhermüller, T., Slep, L. D., Neese, F., Bill, E., Bothe, E., et al. (2004). Nonoxovanadium(IV) and Oxovanadium(V) Complexes with Mixed O, X, O-Donor Ligands (X = S, Se, P, or PO). Inorganic Chemistry, 43(23), 7324-7338. doi:10.1021/ic040052f.

Item is

Files

show Files

Locators

show

Creators

show
hide
 Creators:
Paine, Tapan K.1, Author           
Weyhermüller, Thomas1, Author           
Slep, Leonardo D.1, Author           
Neese, Frank1, Author           
Bill, Eckhard1, Author           
Bothe, Eberhard1, Author           
Wieghardt, Karl1, Author           
Chaudhuri, Phalguni1, Author           
Affiliations:
1Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023881              

Content

show
hide
Free keywords: -
 Abstract: Ligating properties of four potentially tridentate bisphenol ligands containing [O, X, O] donor atoms (X = S 1, Se 2, P 3, or PO 4) toward the vanadium ions in +IV or +V oxidation states have been studied. Each ligand with different heterodonor atoms yields as expected nonoxovanadium(IV) complexes, VIVL2, whose structures have been determined by X-ray diffraction methods as having six-coordinate VIV, VO4X2, core. Compounds 1−4 have also been studied with electrochemical methods, variable-temperature (2−295 K) magnetic susceptibility measurements, X-band electron paramagnetic resonanace (EPR) (2−60 K) spectroscopy, and magnetic circular dichroism (MCD) (5 K) measurements. Electrochemical results suggest metal-centered oxidations to VV (i.e., no formation of phenoxyl radicals from the coordinated phenolates). A combination of density functional theory calculations and experimental EPR investigations indicates a dramatic effect of the heteroatoms on the electronic structure of 1−4 with consequent reordering of the energy levels; 1 and 3 possess a trigonal ground state (dz2)1, but 4 with the phosphoryl oxygen as the heterodonor atom in contrast exhibits a tetragonal ground state, (dxy)1. On the basis of the intense electronic transitions in absorption spectra, all electronic transitions observed for 4 have been assigned to ligand-to-metal charge-transfer transitions, which have been confirmed by preliminary resonance Raman measurements and C/D ratios obtained from low-temperature MCD spectroscopy. Moreover, diamagnetic complexes 5 and 6 containing mononuclear and dinuclear oxovanadium(V) units have also been synthesized and structurally and spectroscopically (51V NMR) characterized.

Details

show
hide
Language(s): eng - English
 Dates: 2004-04-052004-10-202004-11-01
 Publication Status: Published in print
 Pages: 15
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ic040052f
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 43 (23) Sequence Number: - Start / End Page: 7324 - 7338 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669