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Metal-Ligand Bonds

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...

Valence Bond Theory

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...

Structural Isomerism

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...

Coordination Compounds and Nomenclature

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...

Colors and Magnetism

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...

Complexation Equilibria: The Chelate Effect

Complexation Equilibria: The Chelate Effect

In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...

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Related Experiment Video

Updated: Sep 6, 2025

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Published on: May 21, 2019

Robust dicopper(i) μ-boryl complexes supported by a dinucleating naphthyridine-based ligand.

Pablo Ríos¹, Matthew S See¹, Rex C Handford¹

¹Department of Chemistry, University of California Berkeley USA.

Chemical Science

|June 27, 2022

Summary

Researchers isolated stable dicopper(i) boryl complexes using a dinucleating ligand. These complexes demonstrate exceptional thermal stability and play a key role in activating carbon-hydrogen bonds in catalysis.

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Published on: May 21, 2019

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Preparation of SNS CobaltII Pincer Model Complexes of Liver Alcohol Dehydrogenase

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Published on: March 19, 2020

Area of Science:

Organometallic Chemistry
Catalysis
Inorganic Chemistry

Background:

Copper boryl species are crucial reactive intermediates in copper-catalyzed C-H borylation.
Isolation and characterization of these intermediates have been historically challenging.

Purpose of the Study:

To isolate and characterize stable copper boryl complexes.
To investigate the role of these complexes in C-H borylation reactions.
To understand the factors contributing to their stability.

Main Methods:

Synthesis of dicopper(i) boryl complexes using the dinucleating ligand DPFN (2,7-bis(fluoro-di(2-pyridyl)methyl)-1,8-naphthyridine).
Reaction of diboranes with a dicopper(i) alkoxide precursor.
Thermal stability studies in solution.
Reactivity studies focusing on C(sp)-H bond activation.
X-ray diffraction and computational studies for structural and electronic analysis.

Main Results:

Isolation of two thermally stable dicopper(i) boryl complexes: [(DPFN)Cu2(μ-Bpin)][NTf2] and [(DPFN)Cu2(μ-Bcat)][NTf2].
Demonstrated exceptional thermal stability of the boryl complexes in solution up to 100 °C.
Confirmed the role of these complexes in the activation of C(sp)-H bonds.
Detailed structural and electronic descriptions provided via X-ray diffraction and computational methods.

Conclusions:

The dinucleating ligand DPFN is key to the remarkable stability of the isolated dicopper(i) boryl complexes.
These stable complexes serve as valuable intermediates for studying copper-catalyzed C-H borylation.
The findings offer new insights into the mechanism and stability of copper boryl species in catalysis.