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Chemistry of a novel zerovalent ruthenium π-acidic alkene complex, Ru (η (6)-1,3,5-cyclooctatriene)(η (2)-dimethyl fumarate)2.

Mitsudo TA, Ura Y, Kondo T - Proc. Jpn. Acad., Ser. B, Phys. Biol. Sci. (2007)

Bottom Line: Complex 1 was shown to be an excellent mother complex for various zerovalent ruthenium complexes.Complex 1 reacts with amines, phosphines or water to give new zerovalent ruthenium complexes with the ligands.The resulting aqua complexes have a water ligand with an oxygen atom that is a chiral center, i.e., ruthenium complexes with a 'chiral water' ligand were prepared and fully characterized.

View Article: PubMed Central - PubMed

Affiliation: Professor Emeritus, Kyoto University.

ABSTRACT
A novel zerovalent ruthenium complex with a π-acidic ligand, Ru(η (6)-cyclooctatriene)(η (2)-dimethyl fumarate)2 (1), was prepared from Ru(η (4)-cyclooctadiene)(η (6)-cyclooctatriene) [Ru(cod)(cot)]. Complex 1 or Ru(cod)(cot) catalyzes various new carbon-carbon bond-forming reactions that include the [2 + 2] cycloaddition of alkenes and alkynes via ruthenacycles, the creation of a new hydrocarbon, pentacyclo[6.6.0.0(2,6).0(3,13).0(10,14)]tetradeca-4,11-diene [PCTD], by dimerization of 2,5-norbornadiene via C-C bond cleavage, and the codimerization of alkynes and/or alkenes. Complex 1 was shown to be an excellent mother complex for various zerovalent ruthenium complexes. Complex 1 reacts with amines, phosphines or water to give new zerovalent ruthenium complexes with the ligands. The resulting aqua complexes have a water ligand with an oxygen atom that is a chiral center, i.e., ruthenium complexes with a 'chiral water' ligand were prepared and fully characterized.

No MeSH data available.


Reactions of 1 with dppe.
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f12-83_065: Reactions of 1 with dppe.

Mentions: In contrast, the reaction of Ru(cot)(dmfm)2 (1) with 2 equiv of dppe [dppe = 1,2-bis(diphenylphosphino)ethane] in toluene at 50°C for 6 h did not give an analogue of 13, but rather a new complex, Ru(η2-dmfm)(dppe)2 (14), in 66% yield, while treatment of 1 with 0.8 equiv of dppe in toluene at 80 °C for 30 min gave an alkyl alkenyl complex 15 in 81% yield (Scheme 5).25)


Chemistry of a novel zerovalent ruthenium π-acidic alkene complex, Ru (η (6)-1,3,5-cyclooctatriene)(η (2)-dimethyl fumarate)2.

Mitsudo TA, Ura Y, Kondo T - Proc. Jpn. Acad., Ser. B, Phys. Biol. Sci. (2007)

Reactions of 1 with dppe.
© Copyright Policy - open-access
Related In: Results  -  Collection

Show All Figures
getmorefigures.php?uid=PMC3756878&req=5

f12-83_065: Reactions of 1 with dppe.
Mentions: In contrast, the reaction of Ru(cot)(dmfm)2 (1) with 2 equiv of dppe [dppe = 1,2-bis(diphenylphosphino)ethane] in toluene at 50°C for 6 h did not give an analogue of 13, but rather a new complex, Ru(η2-dmfm)(dppe)2 (14), in 66% yield, while treatment of 1 with 0.8 equiv of dppe in toluene at 80 °C for 30 min gave an alkyl alkenyl complex 15 in 81% yield (Scheme 5).25)

Bottom Line: Complex 1 was shown to be an excellent mother complex for various zerovalent ruthenium complexes.Complex 1 reacts with amines, phosphines or water to give new zerovalent ruthenium complexes with the ligands.The resulting aqua complexes have a water ligand with an oxygen atom that is a chiral center, i.e., ruthenium complexes with a 'chiral water' ligand were prepared and fully characterized.

View Article: PubMed Central - PubMed

Affiliation: Professor Emeritus, Kyoto University.

ABSTRACT
A novel zerovalent ruthenium complex with a π-acidic ligand, Ru(η (6)-cyclooctatriene)(η (2)-dimethyl fumarate)2 (1), was prepared from Ru(η (4)-cyclooctadiene)(η (6)-cyclooctatriene) [Ru(cod)(cot)]. Complex 1 or Ru(cod)(cot) catalyzes various new carbon-carbon bond-forming reactions that include the [2 + 2] cycloaddition of alkenes and alkynes via ruthenacycles, the creation of a new hydrocarbon, pentacyclo[6.6.0.0(2,6).0(3,13).0(10,14)]tetradeca-4,11-diene [PCTD], by dimerization of 2,5-norbornadiene via C-C bond cleavage, and the codimerization of alkynes and/or alkenes. Complex 1 was shown to be an excellent mother complex for various zerovalent ruthenium complexes. Complex 1 reacts with amines, phosphines or water to give new zerovalent ruthenium complexes with the ligands. The resulting aqua complexes have a water ligand with an oxygen atom that is a chiral center, i.e., ruthenium complexes with a 'chiral water' ligand were prepared and fully characterized.

No MeSH data available.