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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...

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...

Stereoisomerism

Stereoisomerism

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...

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...

Properties of Organometallic Compounds

Properties of Organometallic Compounds

Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.

Thermal Electrocyclic Reactions: Stereochemistry

Thermal Electrocyclic Reactions: Stereochemistry

The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.

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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

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Published on: May 28, 2014

Dual-Emitting Cyclometalated Platinum Compounds with Isocyanide Ligands.

Craig M Anderson¹, Matthew W Greenberg¹, Christopher N LaFratta¹

¹Department of Chemistry & Biochemistry, Bard College, 30 Campus Road, Annandale-On-Hudson, New York, New York 12504, United States.

|October 27, 2025

Summary

New platinum(II) complexes featuring C^N chelating iminic ligands and diverse isocyanide ligands were synthesized and characterized. These compounds exhibit unique photophysical properties, with thiophene-derived complexes showing distinct dual emission, offering insights into cyclometalated platinum chemistry.

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Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene

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Published on: March 20, 2017

Area of Science:

Organometallic Chemistry
Coordination Chemistry
Materials Science

Background:

Cyclometalated platinum(II) complexes are of interest due to their unique photophysical and electronic properties.
The synthesis of novel platinum(II) compounds with tailored ligands can lead to materials with specific applications.

Purpose of the Study:

To synthesize and characterize novel cyclometalated platinum(II) compounds incorporating both C^N chelating iminic ligands and various isocyanide ligands.
To investigate the photophysical properties of these newly synthesized platinum(II) complexes.
To explore the influence of different HC^N ligand backbones (thiophene vs. benzene) on the spectroscopic and photophysical behavior.

Main Methods:

Synthesis of platinum(II) complexes via reaction of HC^N ligands with [Pt2Me4(μ-SMe2)2] followed by isocyanide ligand substitution.
Characterization using multinuclear NMR spectroscopy, IR spectroscopy, and single-crystal X-ray diffraction (SCXRD).
Photophysical studies involving UV/vis absorption, emission, and transient absorption (TA) spectroscopy, complemented by DFT and TDDFT calculations.

Main Results:

Successful synthesis of square planar platinum(II) complexes with anionic C^N, methyl, and isocyanide ligands.
Thiophene-derived complexes displayed well-resolved dual emission, while benzene-derived complexes showed less resolved bands.
Spectroscopic and computational data provided insights into the electronic structure and photophysical behavior of the complexes.

Conclusions:

The study successfully synthesized and characterized novel cyclometalated platinum(II) complexes with tunable isocyanide ligands.
The nature of the C^N ligand backbone significantly influences the photophysical properties, particularly the emission characteristics.
These findings contribute to the understanding of structure-property relationships in platinum(II) complexes for potential optoelectronic applications.