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Mononuclear and dinuclear complexes with a [Ru(tBu2PCH2CH2PtBu2)(CO)] core
Jose M Goicoechea1, Mary F Mahon, Michael K Whittlesey
1Department of Chemistry, University of Bath, Claverton Down, Bath, UK BA2 7AY.
Dalton Transactions (Cambridge, England : 2003)
|January 27, 2005
Summary
This study details the synthesis and characterization of novel ruthenium complexes, including a five-coordinate species with a unique agostic interaction. These complexes exhibit reactivity with various ligands and undergo water-gas shift chemistry.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Ruthenium Complexes
Background:
- Ruthenium complexes are vital catalysts in various chemical transformations.
- Understanding the reactivity and structural properties of ruthenium carbonyl complexes is crucial for developing new catalytic systems.
Purpose of the Study:
- To synthesize and characterize novel five-coordinate ruthenium complexes.
- To investigate the reactivity of these complexes with different ligands and their potential in water-gas shift chemistry.
Main Methods:
- Thermolysis of solid ruthenium complexes under vacuum.
- X-ray crystallography for structural determination.
- Solution studies using pulsed-gradient spin echo (PGSE) NMR spectroscopy.
- Reactions with various ligands (CO, CH3CN, H2O, DMSO) and silver triflate.
Main Results:
- A five-coordinate ruthenium complex, [Ru(d(t)bpe)(CO)Cl2], was synthesized and shown to possess a remote agostic interaction.
- This complex readily reacts with CO, CH3CN, and H2O to form new adducts.
- Reaction with AgOTf/H2O yielded a tris-aqua complex, which undergoes water-gas shift chemistry in the presence of CO, forming a cationic hydride species and CO2.
- Multiple crystal structures of the synthesized complexes were determined.
Conclusions:
- The study successfully synthesized and characterized a series of novel ruthenium complexes with diverse coordination environments.
- The findings highlight the versatile reactivity of these ruthenium complexes and their potential for catalytic applications, particularly in water-gas shift reactions.