Ruthenium(II) complexes with chiral tetradentate P2N2 ligands catalyze the asymmetric epoxidation of olefins with H2O2

Robert M. Stoop, Stephan Bachmann, Massimiliano Valentini, Antonio Mezzetti

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Abstract

The five-coordinate complexes of the type [RuCl(PNNP)]PF6 (PNNP = tetradentate ligand with a P2N2 donor set) are prepared by chloride abstraction from [RuCl2(PNNP)]. A mixture of Δ-cis-β- and Λ-cis-β-[RuCl2 (1a-κ4P,N,N,P)] (2a; 1a = N, N′-bis[o-(diphenylphosphino)-benzylidene]-2, 2′-diimino-1,1′-(S)-binaphthylene), prepared by reaction of 1a with [RuCl2-(PPh3)3], reacts with Tl[PF6], giving the five-coordinate [RuCl (1a-κ4P,N,N,P)]PF6 (3a). The related trans-[RuCl2(1b-κ4P,N,N,P)] (2b; 1b = N,N′-bis[o-(diphenylphosphino) benzylidene]-(1S,2S)-diiminocyclohexane) reacts with Tl[PF6] to give [RuCl(1b-κ4P,N,N,P)]PF6 (3b). With the amino ligand N,N′-bis[o-(diphenylphosphino) benzylidene]-(1S,2S)-diaminocyclohexane (1c), the aqua complex [RuCl(OH2)(1c-κ4P,N,N,P)]PF6 (5c) is obtained by reaction of Tl-[PF6] with [RuCl2(PPh3) (1c-κ3P,N,N)] (4), which has been isolated and structurally characterized. The reactivity of the five-coordinate 2b with CO and oxygen donors such as water, Et2O, THF, and methanol is reported. Both 3 and 5 catalyze the asymmetric epoxidation of olefins with hydrogen peroxide as oxidant. Enantiomeric excesses up to 42% were obtained in the enantioselective epoxidation of styrene and of other unfunctionalized olefins. The reaction is highly stereospecific, as the epoxidation of (Z)-2-methylstyrene gives a cis:trans ratio of 99:1.

Original languageEnglish
Pages (from-to)4117-4126
Number of pages10
JournalOrganometallics
Volume19
Issue number20
DOIs
Publication statusPublished - Oct 2 2000

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epoxidation
Ruthenium
Epoxidation
Alkenes
ruthenium
alkenes
Ligands
ligands
Styrene
Carbon Monoxide
hydrogen peroxide
Oxidants
styrenes
Hydrogen Peroxide
Methanol
Chlorides
methyl alcohol
reactivity
chlorides
Oxygen

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Ruthenium(II) complexes with chiral tetradentate P2N2 ligands catalyze the asymmetric epoxidation of olefins with H2O2 . / Stoop, Robert M.; Bachmann, Stephan; Valentini, Massimiliano; Mezzetti, Antonio.

In: Organometallics, Vol. 19, No. 20, 02.10.2000, p. 4117-4126.

Research output: Contribution to journalArticle

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title = "Ruthenium(II) complexes with chiral tetradentate P2N2 ligands catalyze the asymmetric epoxidation of olefins with H2O2",
abstract = "The five-coordinate complexes of the type [RuCl(PNNP)]PF6 (PNNP = tetradentate ligand with a P2N2 donor set) are prepared by chloride abstraction from [RuCl2(PNNP)]. A mixture of Δ-cis-β- and Λ-cis-β-[RuCl2 (1a-κ4P,N,N,P)] (2a; 1a = N, N′-bis[o-(diphenylphosphino)-benzylidene]-2, 2′-diimino-1,1′-(S)-binaphthylene), prepared by reaction of 1a with [RuCl2-(PPh3)3], reacts with Tl[PF6], giving the five-coordinate [RuCl (1a-κ4P,N,N,P)]PF6 (3a). The related trans-[RuCl2(1b-κ4P,N,N,P)] (2b; 1b = N,N′-bis[o-(diphenylphosphino) benzylidene]-(1S,2S)-diiminocyclohexane) reacts with Tl[PF6] to give [RuCl(1b-κ4P,N,N,P)]PF6 (3b). With the amino ligand N,N′-bis[o-(diphenylphosphino) benzylidene]-(1S,2S)-diaminocyclohexane (1c), the aqua complex [RuCl(OH2)(1c-κ4P,N,N,P)]PF6 (5c) is obtained by reaction of Tl-[PF6] with [RuCl2(PPh3) (1c-κ3P,N,N)] (4), which has been isolated and structurally characterized. The reactivity of the five-coordinate 2b with CO and oxygen donors such as water, Et2O, THF, and methanol is reported. Both 3 and 5 catalyze the asymmetric epoxidation of olefins with hydrogen peroxide as oxidant. Enantiomeric excesses up to 42{\%} were obtained in the enantioselective epoxidation of styrene and of other unfunctionalized olefins. The reaction is highly stereospecific, as the epoxidation of (Z)-2-methylstyrene gives a cis:trans ratio of 99:1.",
author = "Stoop, {Robert M.} and Stephan Bachmann and Massimiliano Valentini and Antonio Mezzetti",
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T1 - Ruthenium(II) complexes with chiral tetradentate P2N2 ligands catalyze the asymmetric epoxidation of olefins with H2O2

AU - Stoop, Robert M.

AU - Bachmann, Stephan

AU - Valentini, Massimiliano

AU - Mezzetti, Antonio

PY - 2000/10/2

Y1 - 2000/10/2

N2 - The five-coordinate complexes of the type [RuCl(PNNP)]PF6 (PNNP = tetradentate ligand with a P2N2 donor set) are prepared by chloride abstraction from [RuCl2(PNNP)]. A mixture of Δ-cis-β- and Λ-cis-β-[RuCl2 (1a-κ4P,N,N,P)] (2a; 1a = N, N′-bis[o-(diphenylphosphino)-benzylidene]-2, 2′-diimino-1,1′-(S)-binaphthylene), prepared by reaction of 1a with [RuCl2-(PPh3)3], reacts with Tl[PF6], giving the five-coordinate [RuCl (1a-κ4P,N,N,P)]PF6 (3a). The related trans-[RuCl2(1b-κ4P,N,N,P)] (2b; 1b = N,N′-bis[o-(diphenylphosphino) benzylidene]-(1S,2S)-diiminocyclohexane) reacts with Tl[PF6] to give [RuCl(1b-κ4P,N,N,P)]PF6 (3b). With the amino ligand N,N′-bis[o-(diphenylphosphino) benzylidene]-(1S,2S)-diaminocyclohexane (1c), the aqua complex [RuCl(OH2)(1c-κ4P,N,N,P)]PF6 (5c) is obtained by reaction of Tl-[PF6] with [RuCl2(PPh3) (1c-κ3P,N,N)] (4), which has been isolated and structurally characterized. The reactivity of the five-coordinate 2b with CO and oxygen donors such as water, Et2O, THF, and methanol is reported. Both 3 and 5 catalyze the asymmetric epoxidation of olefins with hydrogen peroxide as oxidant. Enantiomeric excesses up to 42% were obtained in the enantioselective epoxidation of styrene and of other unfunctionalized olefins. The reaction is highly stereospecific, as the epoxidation of (Z)-2-methylstyrene gives a cis:trans ratio of 99:1.

AB - The five-coordinate complexes of the type [RuCl(PNNP)]PF6 (PNNP = tetradentate ligand with a P2N2 donor set) are prepared by chloride abstraction from [RuCl2(PNNP)]. A mixture of Δ-cis-β- and Λ-cis-β-[RuCl2 (1a-κ4P,N,N,P)] (2a; 1a = N, N′-bis[o-(diphenylphosphino)-benzylidene]-2, 2′-diimino-1,1′-(S)-binaphthylene), prepared by reaction of 1a with [RuCl2-(PPh3)3], reacts with Tl[PF6], giving the five-coordinate [RuCl (1a-κ4P,N,N,P)]PF6 (3a). The related trans-[RuCl2(1b-κ4P,N,N,P)] (2b; 1b = N,N′-bis[o-(diphenylphosphino) benzylidene]-(1S,2S)-diiminocyclohexane) reacts with Tl[PF6] to give [RuCl(1b-κ4P,N,N,P)]PF6 (3b). With the amino ligand N,N′-bis[o-(diphenylphosphino) benzylidene]-(1S,2S)-diaminocyclohexane (1c), the aqua complex [RuCl(OH2)(1c-κ4P,N,N,P)]PF6 (5c) is obtained by reaction of Tl-[PF6] with [RuCl2(PPh3) (1c-κ3P,N,N)] (4), which has been isolated and structurally characterized. The reactivity of the five-coordinate 2b with CO and oxygen donors such as water, Et2O, THF, and methanol is reported. Both 3 and 5 catalyze the asymmetric epoxidation of olefins with hydrogen peroxide as oxidant. Enantiomeric excesses up to 42% were obtained in the enantioselective epoxidation of styrene and of other unfunctionalized olefins. The reaction is highly stereospecific, as the epoxidation of (Z)-2-methylstyrene gives a cis:trans ratio of 99:1.

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