Related Experiment Video
Updated: Jun 25, 2025

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Cluster dynamics of heterometallic trinuclear clusters during ligand substitution, redox chemistry, and group
Cristin E Juda1, Rex C Handford1, Amymarie K Bartholomew1
1Department of Chemistry and Chemical Biology, Harvard University Cambridge MA 02139 USA betley@chemistry.harvard.edu.
Abstract:
Stepwise metalation of the hexadentate ligand tbsLH6 (tbsLH6 = 1,3,5-C6H9(NHC6H4-o-NHSiMe2tBu)3) affords bimetallic trinuclear clusters (tbsL)Fe2Zn(thf) and (tbsL)Fe2Zn(py). Reactivity studies were pursued to understand metal atom lability as the clusters undergo ligand substitution, redox chemistry, and group transfer processes. Chloride addition to (tbsL)Fe2Zn(thf) resulted in a mixture of species including both all-zinc and all-iron products. Addition of ArN3 (Ar = Ph, 3,5-(CF3)2C6H3) to (tbsL)Fe2Zn(py) yielded a mixture of two trinuclear products: (tbsL)Fe3(μ3-NAr) and (tbsL)Fe2Zn(μ3-NAr)(py). The two imido species were separated via crystallization, and outer sphere reduction of (tbsL)Fe2Zn(μ3-NAr)(py) resulted in the formation of a single product, [2,2,2-crypt(K)][(tbsL)Fe2Zn(μ3-NAr)]. These results provide insight into the relationship between heterometallic cluster structure and substitutional lability and could help inform both future catalyst design and our understanding of metal atom lability in bioinorganic systems.
More Related Videos
06:31Preparation of SNS CobaltII Pincer Model Complexes of Liver Alcohol Dehydrogenase
Published on: March 19, 2020
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
Related Concept Videos
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...
Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
Colors and Magnetism
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: Factors Influencing Stability of Complexes
Valence Bond Theory