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Related Concept Videos

Valence Bond Theory02:42

Valence Bond Theory

Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
Coordination Number and Geometry02:57

Coordination Number and Geometry

For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
Coordination Compounds and Nomenclature02:54

Coordination Compounds and Nomenclature

In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
Metal-Ligand Bonds02:51

Metal-Ligand Bonds

The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
Colors and Magnetism03:02

Colors and Magnetism

Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.
Structural Isomerism02:34

Structural Isomerism

Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...

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Atomic Layer Deposition of Vanadium Dioxide and a Temperature-dependent Optical Model
11:10

Atomic Layer Deposition of Vanadium Dioxide and a Temperature-dependent Optical Model

Published on: May 23, 2018

Low-coordinate and neutral nitrido complexes of vanadium.

Ba L Tran1, Maren Pink, Xinfeng Gao

  • 1Department of Chemistry and the Molecular Structure Center, Indiana University, Bloomington, Indiana 47405, USA.

Journal of the American Chemical Society
|January 19, 2010
PubMed
Summary

New vanadium-nitrido complexes were synthesized from vanadium-azido precursors. These complexes show unique nitrogen atom transfer reactions, forming new ligands and reducing the vanadium center.

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Coordination Chemistry

Background:

  • Vanadium-nitrido complexes are important in catalysis and materials science.
  • The synthesis of novel vanadium-nitrido complexes with specific coordination numbers is of significant interest.

Purpose of the Study:

  • To prepare and characterize neutral, four-coordinate vanadium(V)-nitrido complexes.
  • To investigate the mechanism of nitrogen extrusion from vanadium(III)-azido precursors.
  • To explore the reactivity of the vanadium-nitrido moiety in N-atom transfer reactions.

Main Methods:

  • Thermolysis of metastable vanadium(III)-azido precursors.
  • Multinuclear NMR spectroscopy.
  • Fourier-transform infrared (FT-IR) spectroscopy.
  • Isotopic labeling studies.
  • Single crystal X-ray diffraction.

Main Results:

  • Successfully synthesized two neutral, four-coordinate vanadium(V)-nitrido complexes.
  • Proposed an ordered, early transition state mechanism for N(2) extrusion involving triazametallacycle frameworks.
  • Demonstrated incomplete N-atom transfer to CO and a substituted cyanide, forming bent V-N=C=X ligands.
  • Observed concomitant 2-electron reduction at the vanadium center during N-atom transfer.

Conclusions:

  • The thermolysis of vanadium(III)-azido precursors is an effective route to vanadium(V)-nitrido complexes.
  • The N(2) extrusion mechanism involves specific cyclic transition states.
  • Vanadium-nitrido complexes can participate in unique N-atom transfer reactions, leading to new ligand formations and redox changes.