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Highly electrophilic (salen)ruthenium(VI) nitrido complexes.
Wai-Lun Man1, Tsz-Man Tang, Tsz-Wing Wong
1Department of Biology and Chemistry, City University of Hong Kong, Tat Che Avenue, Hong Kong, China.
Journal of the American Chemical Society
|January 15, 2004
Summary
Cationic ruthenium(VI) nitrido complexes react with amines to form RuIV-hydrazido species. These reactions are significantly faster than analogous osmium nitride reactions, indicating unique reactivity for ruthenium nitrides.
Area of Science:
- Inorganic Chemistry
- Organometallic Chemistry
- Coordination Chemistry
Background:
- Ruthenium nitrido complexes are of interest due to their unique reactivity.
- Salen ligands provide a stable coordination environment for metal centers.
Purpose of the Study:
- To synthesize and characterize cationic ruthenium(VI) nitrido species with salen ligands.
- To investigate the reactivity of these ruthenium nitrido complexes with amines and other nucleophiles.
Main Methods:
- Synthesis of ruthenium(VI) nitrido complexes using [NBun4][RuVI(N)Cl4] and H2L.
- X-ray crystallography to determine the structures of key ruthenium intermediates and products.
- Kinetic studies to elucidate the reaction mechanism with secondary amines.
Main Results:
- Preparation and structural characterization of cationic ruthenium(VI) nitrido species, [RuVI(N)(L)]+.
- Observation of facile N-N coupling to form N2 and Ru(III) species in polar aprotic solvents.
- Rapid reaction with secondary amines to yield Ru(IV)-hydrazido complexes, with a high rate constant for morpholine addition.
- Structural determination of a Ru(IV)-hydrazido complex, [Ru(NHNC4H8)(L)(NHC4H8)]2+.
Conclusions:
- Ruthenium(VI) nitrido complexes with salen ligands exhibit rich reactivity, including N-N coupling and amine addition.
- The high reactivity towards amines, exceeding that of osmium nitrides, highlights the potential of these ruthenium species in synthetic chemistry.
- The formation of Ru(IV)-hydrazido species provides a new pathway for nitrogen-containing ligand synthesis.