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Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus

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Multiple aromatic C-H bond activations by a dirhenium carbonyl complex.

Richard D Adams¹, Poonam Dhull, Jonathan D Tedder

¹Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208, USA. ADAMSRD@mailbox.sc.edu.

Chemical Communications (Cambridge, England)

|March 15, 2018

Summary

Dirhenium complexes achieve aromatic CH activation, forming novel meta-related dimetallated arene rings. Structural and computational analyses confirmed these unique organometallic structures.

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Area of Science:

Organometallic Chemistry
Catalysis
Aromatic Chemistry

Background:

Aromatic CH activation is a key transformation in organic synthesis.
Dirhenium complexes are known catalysts for various reactions.
The formation of dimetallated arene rings is synthetically challenging.

Purpose of the Study:

To explore the capability of a dirhenium complex in aromatic CH activation.
To synthesize and characterize novel meta-related dimetallated arene ring complexes.
To investigate the structural and electronic properties of the resulting complexes.

Main Methods:

Reaction of a dirhenium complex with aromatic substrates.
Single crystal X-ray diffraction for structural determination.
Density Functional Theory (DFT) molecular orbital analyses for electronic structure.

Main Results:

Successful synthesis of two novel complexes: Re2(CO)8(μ-H)(μ-η2-1,2-μ-η2-3,4-C14H8)Re2(CO)8(μ-H) and Re2(CO)8(μ-H)(μ-η1-1,μ-η1-3-C6H4)Re2(CO)8(μ-H).
These complexes feature meta-related dimetallated arene rings.
Structural characterization confirmed the proposed molecular architectures.

Conclusions:

Dirhenium complexes can effectively activate aromatic CH bonds.
This study demonstrates a new route to meta-related dimetallated arene rings.
DFT analyses provide insights into the electronic nature of these organometallic compounds.