Complexes [RuH(η2−H2)P4]BF4 [P = PhP(OEt)2, P(OEt)3, P(OMe)3l react with terminal alkynes HO=CR (R = Ph, p-tolyl, CMe3, SiMe3) to yield alkenes H2C=CHR and [Ru(η3−RC3CHR)P4]+ derivatives. Selective hydrogenation of the alkyne to alkene by the η2−H2 ruthenium catalyst precursor in mild conditions was also observed. The structure of the compound [Ru{η3−(p-tolyl)C3CH(p-tolyl)}{PhP(OEt2}4]BPh4 was determined crystallographically: Space group P21 a = 12.497 (5) Å, b − 24.407 (8) Å, c = 12.763 (5) Å, ß = 96.89 (2)°, Z = 2; final R = 0.057 and Rw = 0.074. The ruthenium atom has a pseudooctahedral coordination with four phosphite groups and the η3−RC3CHR ligand. The [Ru(η3−RC3CHR)P4]+ derivatives react with acetylacetone to afford [Ru(acac)P4]+ cations and organic compounds (Z)-R(H)C=C(H)C≡CR. The reaction of other alkynes [MeO2CC≡CCO2Me, RC=CR (R = Me, Ph)] toward the [RuH(η2−H2)P4]BF4 complexes was also investigated and the synthesis of the vinyl derivatives [Ru{C(CO2Me)=C(H)CO2Me}{PhP-(OEt)2}4]PF6 achieved. Characterization of the complexes by IR and 1H and 31P{1H) NMR spectra is also discussed. © 1991, American Chemical Society. All rights reserved.
REACTIONS OF MOLECULAR-HYDROGEN COMPLEXES [RUH(ETA-2-H2)P4]BF4 WITH ALKYNES - PREPARATION AND CRYSTAL-STRUCTURE OF THE [RU(ETA-3-(PARA-TOLYL)C3CH(PARA-TOLYL))(PHP(OET)2)4]BPH4 DERIVATIVE
ALBERTIN, Gabriele;ANTONIUTTI, Stefano;BORDIGNON, Emilio
1991-01-01
Abstract
Complexes [RuH(η2−H2)P4]BF4 [P = PhP(OEt)2, P(OEt)3, P(OMe)3l react with terminal alkynes HO=CR (R = Ph, p-tolyl, CMe3, SiMe3) to yield alkenes H2C=CHR and [Ru(η3−RC3CHR)P4]+ derivatives. Selective hydrogenation of the alkyne to alkene by the η2−H2 ruthenium catalyst precursor in mild conditions was also observed. The structure of the compound [Ru{η3−(p-tolyl)C3CH(p-tolyl)}{PhP(OEt2}4]BPh4 was determined crystallographically: Space group P21 a = 12.497 (5) Å, b − 24.407 (8) Å, c = 12.763 (5) Å, ß = 96.89 (2)°, Z = 2; final R = 0.057 and Rw = 0.074. The ruthenium atom has a pseudooctahedral coordination with four phosphite groups and the η3−RC3CHR ligand. The [Ru(η3−RC3CHR)P4]+ derivatives react with acetylacetone to afford [Ru(acac)P4]+ cations and organic compounds (Z)-R(H)C=C(H)C≡CR. The reaction of other alkynes [MeO2CC≡CCO2Me, RC=CR (R = Me, Ph)] toward the [RuH(η2−H2)P4]BF4 complexes was also investigated and the synthesis of the vinyl derivatives [Ru{C(CO2Me)=C(H)CO2Me}{PhP-(OEt)2}4]PF6 achieved. Characterization of the complexes by IR and 1H and 31P{1H) NMR spectra is also discussed. © 1991, American Chemical Society. All rights reserved.
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