The planar chiral η6-methyl-o-toluate-ruthenium(II) complex [RuCl2(η6-o-MeC6H4CO2Me)]2 (1) was found to react with (+)-neomenthyldiphenylphosphine (NMDPP) (2) to give monomeric diastereomers [RuCl2(η6-o-MeC6H4CO2Me)-(NMDPP)] (3a and 3b), which were separated by fractional crystallization. Crystals of the less soluble diastereomer 3a belong to the space group P212121, with a 11.998(3), b 16.178(4), c 17.171(4) Å, Z = 4, at 293 K. The structure has been solved by Patterson and Fourier techniques and refined by full-matrix least squares analysis to R = 0.0607, Rw = 0.0624 for 1398 unique reflections with Fo > 2σ(Fo). The ruthenium atoms is pseudo-octahedrally coordinated by η6-methyl-o-toluate, NMDPP and two chloride ligands (RuP 2.357(5), RuCl 2.423(6), 2.381(6) Å). The arene ring is planar within experimental error but it is coordinated unsymmetrically: the RuC distances to the unsubstituted carbon atoms are 2.11(3)–2.17(2) Å, whereas those to the carbon atoms bearing the methoxycarbonyl and methyl groups are 2.26(2) Å and 2.30(2) Å, respectively. The absolute configuration at the chiral planar centre of 3a is R. 3a and 3b have been converted into (R)- and (S)-Ru(η6-o-MeC6H4CO2Me)(η4-1,5-cyclooctadiene) (6a and 6b respectively), from which the (R,R)- and (S,S)-[RuCl2(η6-o-MeC6H4CO2Me)]2 have been obtained in enantiomeric purities of 90 and 60%, respectively.

Resolution of the chiral eta-6-methyl-o-toluate complex [RuCl2 (eta-6-o-MeC6H4CO2Me)]2. Crystal structure and absolute configuration of the (+)-neomenthyldiphenylphosphine (NMDPP) complex RuCl2(eta-6-o-MeC6H4CO2Me)-[(+)-NMDPP]

MARCHETTI, FABIO;LAZZARONI, RAFFAELLO;VITULLI, GIOVANNI;
1989

Abstract

The planar chiral η6-methyl-o-toluate-ruthenium(II) complex [RuCl2(η6-o-MeC6H4CO2Me)]2 (1) was found to react with (+)-neomenthyldiphenylphosphine (NMDPP) (2) to give monomeric diastereomers [RuCl2(η6-o-MeC6H4CO2Me)-(NMDPP)] (3a and 3b), which were separated by fractional crystallization. Crystals of the less soluble diastereomer 3a belong to the space group P212121, with a 11.998(3), b 16.178(4), c 17.171(4) Å, Z = 4, at 293 K. The structure has been solved by Patterson and Fourier techniques and refined by full-matrix least squares analysis to R = 0.0607, Rw = 0.0624 for 1398 unique reflections with Fo > 2σ(Fo). The ruthenium atoms is pseudo-octahedrally coordinated by η6-methyl-o-toluate, NMDPP and two chloride ligands (RuP 2.357(5), RuCl 2.423(6), 2.381(6) Å). The arene ring is planar within experimental error but it is coordinated unsymmetrically: the RuC distances to the unsubstituted carbon atoms are 2.11(3)–2.17(2) Å, whereas those to the carbon atoms bearing the methoxycarbonyl and methyl groups are 2.26(2) Å and 2.30(2) Å, respectively. The absolute configuration at the chiral planar centre of 3a is R. 3a and 3b have been converted into (R)- and (S)-Ru(η6-o-MeC6H4CO2Me)(η4-1,5-cyclooctadiene) (6a and 6b respectively), from which the (R,R)- and (S,S)-[RuCl2(η6-o-MeC6H4CO2Me)]2 have been obtained in enantiomeric purities of 90 and 60%, respectively.
Salvadori, P; Pertici, P; Marchetti, Fabio; Lazzaroni, Raffaello; Vitulli, Giovanni; Bennett, A.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11568/8565
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