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Vanadium: Inorganic & Coordination Chemistry

  1. Raymond L. Richards

Published Online: 15 DEC 2011

DOI: 10.1002/9781119951438.eibc0236

Encyclopedia of Inorganic and Bioinorganic Chemistry

Encyclopedia of Inorganic and Bioinorganic Chemistry

How to Cite

Richards, R. L. 2011. Vanadium: Inorganic & Coordination Chemistry . Encyclopedia of Inorganic and Bioinorganic Chemistry. .

Author Information

  1. University of Sussex, Brighton, UK

Publication History

  1. Published Online: 15 DEC 2011


The chemistry of vanadium and its complexes with various ligands is reviewed, following the format used in the corresponding article in the first edition of this Encyclopedia. The article begins with an update of the element itself. This is followed by a description of the binary compounds formed with hydride, halide, oxide, chalcogenide, nitride, and phosphide ligands. Compounds formed with carbide ligands are briefly mentioned, but thereafter carbon-donor ligands are not included in this article.

Then follows a review of the coordination chemistry of vanadium, which, after a brief introduction, is grouped into sections according to the oxidation state of vanadium in the compounds under discussion. The first section describes compounds in low oxidation states, [vanadium(−1), vanadium(0), and vanadium(1)], in which nitrogen-donor ligands such as N2 and NO and tertiary phosphine ligands are prominent. The second section describes the coordination chemistry of vanadium(II). This section is subdivided according to the donor atom of the various ligands that bind the metal, that is, oxygen, nitrogen, and phosphorus ligands and other ligand types, such as halides. Vanadium(III) coordination complexes comprise the next section, which is subdivided according to oxygen ligands, nitrogen ligands, sulfur ligands, and halide and other ligands. It is to be noted that in general the compounds that have thus far been described tend to be oxidized rather easily to compounds of higher oxidation states.

The coordination chemistry of vanadium(IV), which comprises the next section, is dominated by the very stable VO2+ (vanadyl) group and a separate subsection is devoted to coordination compounds that contain this grouping. The other subsections describe nonoxo complexes and halide, nitrogen, and sulfur and selenium ligands; the thiovanadyl group, VS2+ is included in the last subsection. Oxygen-donor ligands are also prominent in the chemistry of the highest oxidation state of vanadium(V), whose coordination chemistry is covered in the final section. Thus, separate subsections describe the coordination chemistry of the VO3+ group, the VO2+ unit, and peroxo-complexes. The remaining subsections describe nonoxo complexes, nitrogen, sulfur, and selenium ligands.

A feature of the development of vanadium chemistry during the years since the original article appeared has been the very large increase in the number of coordination complexes that have been prepared and structurally characterized. The content and relative sizes of the subsections of this article and the figures that are included reflect this trend.


  • vanadium;
  • vanadyl;
  • coordination compounds;
  • hydride;
  • oxide;
  • halide;
  • chalcogenide;
  • N, O, S, Se, and P-donor ligands;
  • X-ray structures;
  • spectroscopy