Related Experiment Video
Updated: Jun 1, 2026

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
On the Ability of Bismuth to Couple Weakly Coordinating Anions
Lucas Mele1, Reena Balhara1, Dimitrios A Pantazis1
1Max-Planck-Institut Für Kohlenforschung, Mülheim an der Ruhr, Germany.
Abstract:
Similar to aryldiazonium salts, hypervalent bismuth species have been shown to promote coupling of weakly coordinating anions (WCAs) such as triflate and tetrafluoroborate. In this study, we identify the origin of the driving force for these transformations by quantifying scalar relativistic effects in high‑valent bismuth chemistry. All‑electron DFT comparisons between relativistic and non‑relativistic limits reveal pronounced stabilization of the Bi 6s orbital in the former framework. As a result, the structure and frontier‑orbital energetics of the Bi(V)/Bi(III) processes are heavily affected, thus having a pronounced effect on the reductive elimination. Specifically, relativistic contributions to Bi could be observed on different scales ranging from a simple monoatomic model to complex reaction profiles. These results rationalize the facile WCA coupling from catalytically relevant Bi(V) complexes and establish the basis of why Bi(III) is an exceptionally potent nucleofuge in bismuth‑mediated bond formation.
More Related Videos
11:04Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides
Published on: September 7, 2019
14:44Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR
Published on: December 16, 2013
Related Concept Videos
Valence Bond Theory
Metal-Ligand Bonds
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...
Structural Isomerism
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...
Complexation Equilibria: Factors Influencing Stability of Complexes
Coordination Compounds and Nomenclature
Complexation Equilibria: Overview
The equilibrium constant of the complexation reaction is represented as the formation constant...