Related Experiment Video
Updated: Aug 6, 2026
10:57
Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction
Published on: April 10, 2018
Dinitrogen chemistry from trigonally coordinated iron and cobalt platforms
Theodore A Betley1, Jonas C Peters
1Division of Chemistry and Chemical Engineering, Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125, USA.
Journal of the American Chemical Society
|September 4, 2003
Summary
This study introduces novel iron and cobalt complexes supporting diverse ligands. These findings offer new pathways for synthesizing transition metal compounds with unique electronic properties.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Inorganic Chemistry
Background:
- Trigonally coordinated metal platforms are crucial in catalysis and materials science.
- Understanding ligand binding and reactivity in low-coordinate metal complexes is an ongoing challenge.
Purpose of the Study:
- To synthesize and characterize novel trigonally coordinated iron and cobalt complexes.
- To investigate the reactivity of these complexes with pi-acidic and pi-basic ligands.
- To explore new synthetic routes to transition metal compounds.
Main Methods:
- Synthesis of trigonally coordinated iron and cobalt complexes with a [PhBPiPr3] ligand framework.
- Characterization using spectroscopic and crystallographic techniques.
- Reactions involving N2, NR, and RN3 ligands to explore coordination and reactivity.
Main Results:
- First thoroughly characterized 4-coordinate iron(0) complexes with N2 ligands were obtained.
- Methylation of N2 ligands yielded iron(II) and cobalt(II) diazenido products.
- Oxidation of mononuclear species led to dinuclear complexes, enabling access to the [PhBPiPr3]MI subunit.
- Reaction with organic azides resulted in oxidative nitrene transfer and N2 release.
Conclusions:
- The [PhBPiPr3]M platform (M = Fe, Co) effectively supports both pi-acidic (N2) and pi-basic (NR) ligands.
- Novel synthetic methodologies were developed for accessing low-coordinate iron and cobalt complexes.
- These complexes serve as versatile precursors for further chemical transformations, including oxidative nitrene transfer.
More Related Videos
Related Concept Videos
02:54Coordination 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...
02:51Metal-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...
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...
02:57Coordination 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.
02:34Structural 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...
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...
02:42Valence 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...
01:22Inorganic Nitrogen Assimilation
Nitrogen is an essential element in biological systems, forming a crucial component of proteins, nucleic acids, and other cellular constituents. Many bacteria and archaea acquire nitrogen in the form of nitrate (NO₃⁻) or ammonia (NH₃), which are then assimilated into biomolecules through specific enzymatic pathways.Assimilatory Nitrate ReductionWhen nitrate enters the cell, it undergoes a two-step reduction process known as assimilatory nitrate reduction. Initially, the enzyme nitrate reductase...