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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.


Atom numbering of 18 and 19.
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f6-83_065: Atom numbering of 18 and 19.

Mentions: Complex 18 is a binuclear Ru(II) aqua complex in which (S,S)-DIPAMP ligands coordinate to the ruthenium centers in a facial tridentate manner. Notably, oxaruthenacycle structures are formed via the apparent cleavage of an O–CH3 bond in dimethyl fumarate.(17)In the component of 18 shown on the left-hand side of the structure in Fig. 6, the water oxygen atom O1 is located at a trans position relative to the phosphorus atom P2, and the sp3 carbon atom C1 in the oxametallacycle moiety is trans to O5. On the other hand, in the component on the right-hand side, while (S,S)-DIPAMP coordinates in the same manner, the position of the oxametallacycle relative to the (S,S)-DIPAMP ligand is different from that in the component on the left side; i.e., in the right-hand component, the oxygen atom of the oxaruthenacycle O7 is located trans to the phosphorus atom P3, to give a noncoordinated methoxyphenyl group. The carbonyl oxygen atom O3 is bound to Ru2, and the coordinated water molecule is connected to two different carbonyl oxygen atoms O4 and O6. The distances O1· · ·O4 and O1· · ·O6 are 2.820(11) and 2.701(11) Å, which indicates the presence of hydrogen bonds between H1· · · O4 and H2· · · O6, respectively. Overall, the aggregation of the two P-P-O ligated oxaruthenacycle moieties is stabilized by coordination of the carbonyl oxygen and the hydrogen bond H2· · · O6. The oxygen atom of the water molecule O1 can be considered a chiral center in the solid state, since it has four different groups, i.e. ruthenium, an unshared electron pair, and two protons with different hydrogen bonds, as was observed in complexes 16.26)


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)

Atom numbering of 18 and 19.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

f6-83_065: Atom numbering of 18 and 19.
Mentions: Complex 18 is a binuclear Ru(II) aqua complex in which (S,S)-DIPAMP ligands coordinate to the ruthenium centers in a facial tridentate manner. Notably, oxaruthenacycle structures are formed via the apparent cleavage of an O–CH3 bond in dimethyl fumarate.(17)In the component of 18 shown on the left-hand side of the structure in Fig. 6, the water oxygen atom O1 is located at a trans position relative to the phosphorus atom P2, and the sp3 carbon atom C1 in the oxametallacycle moiety is trans to O5. On the other hand, in the component on the right-hand side, while (S,S)-DIPAMP coordinates in the same manner, the position of the oxametallacycle relative to the (S,S)-DIPAMP ligand is different from that in the component on the left side; i.e., in the right-hand component, the oxygen atom of the oxaruthenacycle O7 is located trans to the phosphorus atom P3, to give a noncoordinated methoxyphenyl group. The carbonyl oxygen atom O3 is bound to Ru2, and the coordinated water molecule is connected to two different carbonyl oxygen atoms O4 and O6. The distances O1· · ·O4 and O1· · ·O6 are 2.820(11) and 2.701(11) Å, which indicates the presence of hydrogen bonds between H1· · · O4 and H2· · · O6, respectively. Overall, the aggregation of the two P-P-O ligated oxaruthenacycle moieties is stabilized by coordination of the carbonyl oxygen and the hydrogen bond H2· · · O6. The oxygen atom of the water molecule O1 can be considered a chiral center in the solid state, since it has four different groups, i.e. ruthenium, an unshared electron pair, and two protons with different hydrogen bonds, as was observed in complexes 16.26)

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.