Related Experiment Video
Updated: Feb 16, 2026
07:14
Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
3.8K
Hydrogen Atom Transfer by a High-Valent Nickel-Chloride Complex
Prasenjit Mondal1, Paolo Pirovano1, Ankita Das1
1School of Chemistry and CRANN/AMBER Nanoscience Institute, Trinity College Dublin, The University of Dublin , College Green, Dublin 2, Ireland.
Journal of the American Chemical Society
|January 3, 2018
Summary
High-valent nickel-halide complexes were synthesized and characterized. These complexes activate C-H bonds via a hydrogen atom transfer mechanism, offering insights into enzymatic oxidants and new catalyst designs.
Area of Science:
- Inorganic Chemistry
- Catalysis
- Biomimetic Chemistry
Background:
- Oxo-metal-halide complexes are known C-H bond activating oxidants.
- The electrophilic reactivity of metal-halide species remains largely unexplored.
Purpose of the Study:
- To investigate the electrophilic reactivity of metal-halide species.
- To synthesize and characterize a high-valent nickel-halide complex.
- To elucidate the mechanism of C-H bond activation by this complex.
Main Methods:
- Synthesis of a high-valent nickel-halide complex [NiIII(Cl)(L)] (2).
- Characterization using electronic absorption, EPR, XAS, and mass spectrometry.
- Kinetic studies analyzing Hammett, Evans-Polanyi, and Marcus relationships.
Main Results:
- Complex 2 was successfully synthesized and characterized.
- Complex 2 readily reacted with phenolic O-H and hydrocarbon C-H bonds.
- Kinetic analysis revealed a hydrogen atom transfer (HAT) mechanism for C-H activation.
Conclusions:
- The study demonstrates the electrophilic reactivity of metal-halide species.
- Findings provide insights into enzymatic high-valent oxo-metal-halide oxidants.
- Opens new avenues for designing oxidative halogenation catalysts.
Related Concept Videos
00:26Hydrogen Bonds
134.8K
Hydrogen bonds are weak attractions between atoms that have formed other chemical bonds. One of these atoms is electronegative, like oxygen, and has a partial negative charge. The other is a hydrogen atom that has bonded with another electronegative atom and has a partial positive charge.
Hydrogen Bonds Control the World!
Because hydrogen has very weak electronegativity when it binds with a strongly electronegative atom, such as oxygen or nitrogen, electrons in the bond are unequally shared....
Hydrogen Bonds Control the World!
Because hydrogen has very weak electronegativity when it binds with a strongly electronegative atom, such as oxygen or nitrogen, electrons in the bond are unequally shared....
134.8K
01:04Hydrogen Bonds
15.2K
A hydrogen bond is formed when a weakly positive hydrogen atom already bonded to one electronegative atom (for example, the oxygen in the water molecule) is attracted to another electronegative atom from another polar molecule, such as water (H2O), hydrogen fluoride (HF), or ammonia (NH3). The huge electronegativity difference between the H atom (2.1) and the atom to which it is bonded (4.0 for an F atom, 3.5 for an O atom, or 3.0 for an N atom), combined with the very small size of an H atom...
15.2K
02:44Atomic Orbitals
45.4K
An atomic orbital represents the three-dimensional regions in an atom where an electron has the highest probability to reside. The radial distribution function indicates the total probability of finding an electron within the thin shell at a distance r from the nucleus. The atomic orbitals have distinct shapes which are determined by l, the angular momentum quantum number. The orbitals are often drawn with a boundary surface, enclosing densest regions of the cloud.
45.4K
02:59The Atomic Theory of Matter
130.8K
The earliest recorded discussion of the basic structure of matter comes from ancient Greek philosophers. Leucippus and Democritus argued that all matter was composed of small, finite particles that they called atomos, meaning “indivisible.” Later, Aristotle and others came to the conclusion that matter consisted of various combinations of the four “elements” — fire, earth, air, and water — and could be infinitely divided. Interestingly, these philosophers...
130.8K
03:24Hybridization of Atomic Orbitals I
68.0K
The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals. The new orbitals that...
68.0K
03:35Hybridization of Atomic Orbitals II
49.4K
sp3d and sp3d 2 Hybridization
49.4K