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Cyclopentadiene-mediated hydride transfer from rhodium complexes

C L Pitman¹, O N L Finster¹, A J M Miller¹

¹Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290, USA. ajmm@email.unc.edu.

Chemical Communications (Cambridge, England)

|March 8, 2016

Summary

Researchers explored rhodium hydride complexes but isolated a pentamethylcyclopentadiene complex instead. This complex demonstrated significant hydride transfer capabilities, including the reduction of nicotinamide adenine dinucleotide (NAD(+)).

Area of Science:

Organometallic Chemistry
Catalysis
Biochemistry

Background:

Rhodium complexes are crucial in catalysis.
Understanding catalytic intermediates is key to reaction design.
Hydride transfer is a fundamental reaction in organic and biological chemistry.

Purpose of the Study:

To synthesize a proposed rhodium hydride catalytic intermediate.
To characterize the unexpected product formed.
To investigate the hydride transfer capabilities of the isolated complex.

Main Methods:

Synthesis of organometallic complexes.
Characterization using spectroscopic methods.
Thermodynamic analysis of hydride transfer.
Experimental hydride transfer reactions.

Main Results:

Isolation of (Cp*H)Rh(bpy)Cl, a pentamethylcyclopentadiene rhodium complex.
Confirmation of C-H bond-forming reductive elimination from a rhodium hydride precursor.
Demonstration of the complex's ability to transfer hydride.
Successful reduction of nicotinamide adenine dinucleotide (NAD(+)) using the complex.

Conclusions:

The study identified an unexpected stable complex instead of the targeted rhodium hydride.
The isolated complex exhibits valuable hydride transfer properties.
This finding offers new insights into rhodium-mediated reactions and potential applications in redox chemistry.

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