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Properties of Organometallic Compounds

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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.

Heterogeneous Catalysis

Heterogeneous Catalysis

Heterogeneous catalysis involves a catalyst in a different phase from the reactants. It is a process where the catalyst and the reactants are in distinct phases, typically solid and gas or liquid.Most heterogeneous catalysts are metals, metal oxides, or acids. The list includes transition metals like iron (Fe), cobalt (Co), nickel (Ni), palladium (Pd), platinum (Pt), chromium (Cr), manganese (Mn), tungsten (W), silver (Ag), and copper (Cu). These metals possess partially vacant d orbitals that...

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The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
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Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

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Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...

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Cyclometalated Platinum Compounds from Competing C-H/C-X Bond Activation Pathways.

Craig M Anderson¹, Matthew W Greenberg¹, Christopher N LaFratta¹

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

|March 23, 2026

Summary

Reactions of platinum(II) precursors with X-C^N^N ligands yielded platinum(IV) and platinum(II) compounds. The platinum(II) product resulted from C-H activation and methane elimination, confirmed by spectroscopy and DFT calculations.

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Area of Science:

Organometallic Chemistry
Coordination Chemistry
Photochemistry

Background:

Platinum complexes are vital in catalysis and materials science.
Understanding reactivity pathways of platinum precursors is crucial for designing new functional molecules.
Cyclometalated ligands offer unique electronic and steric properties.

Purpose of the Study:

To investigate the reactivity of [Pt2Me4(μ-SMe2)2] with X-C^N^N ligands (X = Br, Cl).
To characterize the resulting platinum(IV) and platinum(II) products.
To explore the photophysical properties and reaction mechanisms using computational methods.

Main Methods:

Synthesis of platinum complexes.
Multinuclear NMR spectroscopy and single-crystal X-ray diffraction (SCXRD) for structural characterization.
UV/vis, emission, and transient absorption (TA) spectroscopies for photophysical studies.
Density Functional Theory (DFT) and Time-Dependent DFT (TD-DFT) calculations.

Main Results:

Reaction with X=Br yielded a six-coordinate cyclometalated platinum(IV) complex with an anionic C^N^N ligand.
Reaction with X=Cl produced both platinum(IV) and platinum(II) products.
The platinum(II) species formed via C-H activation and reductive elimination of methane.
Experimental and computational results were compared to elucidate reaction pathways.

Conclusions:

The reactivity of platinum precursors is sensitive to the nature of the ancillary ligand (X-C^N^N).
C-H activation is a viable pathway for forming platinum(II) species from platinum(IV) intermediates.
Spectroscopic and computational methods provide complementary insights into complex reaction mechanisms.