Reversible CO binding at a nickel complex supported by an ambiphilic PBiP tridentate ligand
Dagyum Yoo1, Alexander C Brannan1, Soohyun Lim1
1Department of Chemistry, Seoul National University, Seoul 08826, Republic of Korea. heuibeomlee@snu.ac.kr.
Chemical Communications (Cambridge, England)
|June 30, 2025
Summary
A novel nickel complex with a bismuthide ligand reversibly binds carbon monoxide (CO), showcasing metal-ligand cooperation. Chloride migration to bismuth highlights the unique properties of organobismuth compounds in catalysis.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Inorganic Chemistry
Background:
- Metal-ligand cooperation is crucial for catalytic activity.
- Organobismuth compounds offer unique electronic properties.
- Nickel complexes are widely studied in catalysis.
Purpose of the Study:
- To investigate the carbon monoxide (CO) binding of a nickel complex supported by a bismuthide diphosphine tridentate ligand.
- To explore the mechanism of metal-ligand cooperative transformations.
- To understand the role of organobismuth donors in chemical reactions.
Main Methods:
- Synthesis of a nickel chloride complex with a bismuthide diphosphine tridentate ligand.
- Reversible carbon monoxide binding studies.
- Spectroscopic and structural analysis to elucidate the reaction mechanism.
Main Results:
- The nickel complex reversibly binds CO, forming a nickel dicarbonyl species.
- Chloride migration to the bismuth center was observed during CO binding.
- Substitution of chloride with nitroxide inhibited CO dissociation, weakening the Ni-Bi interaction.
Conclusions:
- The study demonstrates metal-ligand cooperative CO binding in a nickel-bismuth system.
- Organobismuth donors exhibit ambiphilicity, facilitating chloride migration.
- The Ni-Bi interaction strength influences CO dissociation, offering insights into catalyst design.
Related Concept Videos
02:51Metal-Ligand Bonds
21.5K
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...
21.5K
02:42Valence Bond Theory
9.7K
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...
9.7K
02:34Structural Isomerism
19.7K
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...
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...
19.7K
01:19Complexation Equilibria: The Chelate Effect
681
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...
681
03:02Colors and Magnetism
12.3K
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...
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...
12.3K
02:36Regioselectivity and Stereochemistry of Hydroboration
8.4K
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
8.4K