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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.


Mechanism of the fomation of 18 or 19.
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f15-83_065: Mechanism of the fomation of 18 or 19.

Mentions: A possible pathway to 18 and 19 based on our previous investigation of the reactivity of Ru(cot)(dmfm)2 (1) is proposed in Scheme 8. The reaction of 1 with a P-P-O ligand and H2O would give the Ru(0) aqua complex 20 via Ru(η4-cot)(dmfm)(η2-P-P-O) and Ru(η2-cot)(dmfm)(η3-PP-O). The structure of 20 is partially similar to that of 16, but the ruthenium center is more electron-rich, and thus oxidative addition of the coordinated H2O would proceed and subsequent insertion of dimethyl fumarate into the formed Ru-H bond would give alkyl hydroxo intermediate 22. From 22, nucleophilic attack of H2O toward the carbonyl carbon with the assistance of ruthenium, which acts as a Lewis acid, and the loss of MeOH would give the oxaruthenacycle aqua complex 25, corresponding to the left-hand component of 18. Liberation of H2O from 25 and migration of the oxaruthenacycle moiety would give the coordinatively unsaturated 16-electron moiety of the right-hand component of 18, which finally combines with 25 to afford 18.


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)

Mechanism of the fomation of 18 or 19.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

f15-83_065: Mechanism of the fomation of 18 or 19.
Mentions: A possible pathway to 18 and 19 based on our previous investigation of the reactivity of Ru(cot)(dmfm)2 (1) is proposed in Scheme 8. The reaction of 1 with a P-P-O ligand and H2O would give the Ru(0) aqua complex 20 via Ru(η4-cot)(dmfm)(η2-P-P-O) and Ru(η2-cot)(dmfm)(η3-PP-O). The structure of 20 is partially similar to that of 16, but the ruthenium center is more electron-rich, and thus oxidative addition of the coordinated H2O would proceed and subsequent insertion of dimethyl fumarate into the formed Ru-H bond would give alkyl hydroxo intermediate 22. From 22, nucleophilic attack of H2O toward the carbonyl carbon with the assistance of ruthenium, which acts as a Lewis acid, and the loss of MeOH would give the oxaruthenacycle aqua complex 25, corresponding to the left-hand component of 18. Liberation of H2O from 25 and migration of the oxaruthenacycle moiety would give the coordinatively unsaturated 16-electron moiety of the right-hand component of 18, which finally combines with 25 to afford 18.

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.