Related Experiment Video
Updated: Aug 26, 2025
08:25
Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs
Published on: January 17, 2020
7.3K
Chirality-Guided Isomerization of Mn2S2 Diamond Core Complexes: A Mechanistic Study
Trung H Le1, Hao Nguyen1, Heather A Arnold1
1Department of Chemistry, Texas A&M University, College StationTexas77845, United States.
Inorganic Chemistry
|October 4, 2022
Summary
Researchers discovered a new class of manganese-sulfur complexes, the Mn2S2 rhombs. They found these complexes can exist as syn- and anti-isomers in solution, interconverting via monomeric intermediates.
Area of Science:
- Inorganic Chemistry
- Organometallic Chemistry
- Coordination Chemistry
Background:
- A ligand transfer discovery prompted the study of dimanganese complexes with Mn2S2 rhombs.
- This class of complexes, featuring tethered and non-tethered ligands, was previously under-studied.
- Understanding the structural and isomeric properties of these complexes is crucial.
Purpose of the Study:
- To synthesize and characterize novel dimanganese complexes containing Mn2S2 rhombs.
- To investigate the isomeric forms (syn and anti) of these complexes in solution and solid-state.
- To elucidate the mechanism of interconversion between syn and anti isomers.
Main Methods:
- Synthesis of tethered and non-tethered dimanganese complexes.
- Solid-state structural analysis.
- Fourier-transform infrared (FTIR) spectroscopy.
- Theoretical frequency calculations.
- Molecular scrambling experiments.
- Density functional theory (DFT) analysis.
- Kinetic studies.
Main Results:
- A tethered dimanganese complex with a H2N2S2 ligand and Mn2S2 rhomb was synthesized.
- The non-tethered analogue adopted an anti-conformation in the solid-state.
- Spectroscopic and computational analyses revealed the coexistence and interconversion of syn and anti isomers in solution.
- The anti-form exists as RS isomers, while the syn-form is restricted to RR or SS configurations.
- Monomeric, pentacoordinate, 16-electron intermediates were identified, facilitating isomer interconversion.
Conclusions:
- The study characterizes a new class of Mn2S2 rhomb complexes.
- Isomerization between syn and anti forms occurs in solution via reversible dissociation into monomeric intermediates.
- The findings provide insights into the dynamic behavior and structural diversity of dimanganese complexes.
More Related Videos
Related Concept Videos
02:52Stereoisomerism
12.3K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
12.3K
02:05Prochirality
3.9K
The concept of prochirality leads to the nomenclature of the individual faces of a molecule and plays a crucial role in the enantioselective reaction. It is a concept where two or more achiral molecules react to produce chiral products. A typical process is the reaction of an achiral ketone to generate a chiral alcohol. Here, the achiral reactant reacts with an achiral reducing agent, sodium borohydride, to generate an equimolar mixture of the chiral enantiomers of the product. For example, an...
3.9K
02:30Chirality at Nitrogen, Phosphorus, and Sulfur
5.9K
Chirality is most prevalent in carbon-based tetrahedral compounds, but this important facet of molecular symmetry extends to sp3-hybridized nitrogen, phosphorus and sulfur centers, including trivalent molecules with lone pairs. Here, the lone pair behaves as a functional group in addition to the other three substituents to form an analogous tetrahedral center that can be chiral.
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
5.9K
02:33Stereoisomerism of Cyclic Compounds
9.1K
In this lesson, we delve into the role of ring conformation and its stability, which determines the spatial arrangement and, consequently, the molecular symmetry and stereoisomerism of cyclic compounds. 1,2-Dimethylcyclohexane is used as a case study to evaluate the possible number of stereoisomers. Here, given the multiple (n = 2) chiral centers, there are 2n = 4 possible configurations that lack a plane of symmetry, as the ring skeleton exists in a non-planar chair conformation. In addition,...
9.1K
02:25Molecules with Multiple Chiral Centers
12.0K
Molecules that possess multiple chiral centers can afford a large number of stereoisomers. For instance, while some molecules like 2-butanol have one chiral center, defined as a tetrahedral carbon atom with four different substituents attached, several molecules like butane-2,3-diol have multiple chiral centers. A simple formula to predict the number of stereoisomers possible for a molecule with n chiral centers is 2n. However, there can be a lower number where some of the stereoisomers are...
12.0K
02:25Chirality
24.9K
Chirality is a term that describes the lack of mirror symmetry in an object. In other words, chiral objects cannot be superposed on their mirror images. For example, our feet are chiral, as the mirror image of the left foot, the right foot, cannot be superposed on the left foot.
Chiral objects exhibit a sense of handedness when they interact with another chiral object. For example, our left foot can only fit in the left shoe and not in the right shoe. Achiral objects — objects that have...
Chiral objects exhibit a sense of handedness when they interact with another chiral object. For example, our left foot can only fit in the left shoe and not in the right shoe. Achiral objects — objects that have...
24.9K