Synthesis and reactivity of 2-aminoethanethiolato-bridged dinuclear Ru(hmb) complexes (hmb = η6-hexamethylbenzene): Mechanistic consideration on transfer hydrogenation with bifunctional [RuCl 2(hmb)]2/2-aminoethanethiol catalyst system

Masato Ito; Akira Watanabe; Yuji Shibata; Takao Ikariya

doi:10.1021/om100773a

Synthesis and reactivity of 2-aminoethanethiolato-bridged dinuclear Ru(hmb) complexes (hmb = η⁶-hexamethylbenzene): Mechanistic consideration on transfer hydrogenation with bifunctional [RuCl ₂(hmb)]₂/2-aminoethanethiol catalyst system

Masato Ito, Akira Watanabe, Yuji Shibata, Takao Ikariya

Research output: Contribution to journal › Article › peer-review

21 Citations (Scopus)

Abstract

A series of dinuclear Ru(hmb) complexes with a bridging 2-aminoethanethiolato ligand (S-NH) have been newly prepared by controlling the stoichiometry of starting materials. Their catalytic performance in the racemization of an optically pure secondary alcohol indicated that the relative proportion of the Ru(hmb) and the S-NH unit in these catalyst precursors in addition to the amount of base as an activating agent is crucially important to generate a catalytically active species. Moreover, chiral versions of dinuclear Ru(S-NH)(hmb) complexes displayed excellent catalytic performance in terms of reactivity and enantioselectivity for the asymmetric transfer hydrogenation of aromatic ketones using HCO₂H-N(C₂H₅) ₃. In agreement with these results, the crossover experiment using a symmetrically bridged dinuclear complex, [Ru(μ-SCH₂CH ₂NH₂)(hmb)]₂Cl₂, and its Cp*Ir dinuclear congener, [Cp*Ir(μ-SCH₂CH₂NH ₂)]₂Cl₂ (Cp* = η⁵-C ₅(CH₃)₅), suggested that the catalytic performance in the hydrogen transfer is originated from the mononuclear amido complex Ru(SCH₂CH₂NH)(hmb) bearing a Ru/NH bifunctionality.

Original language	English
Pages (from-to)	4584-4592
Number of pages	9
Journal	Organometallics
Volume	29
Issue number	20
DOIs	https://doi.org/10.1021/om100773a
Publication status	Published - Oct 25 2010
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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Synthesis and reactivity of 2-aminoethanethiolato-bridged dinuclear Ru(hmb) complexes (hmb = η⁶-hexamethylbenzene): Mechanistic consideration on transfer hydrogenation with bifunctional [RuCl ₂(hmb)]₂/2-aminoethanethiol catalyst system. / Ito, Masato; Watanabe, Akira; Shibata, Yuji et al.
In: Organometallics, Vol. 29, No. 20, 25.10.2010, p. 4584-4592.

Research output: Contribution to journal › Article › peer-review

Ito, M, Watanabe, A, Shibata, Y & Ikariya, T 2010, 'Synthesis and reactivity of 2-aminoethanethiolato-bridged dinuclear Ru(hmb) complexes (hmb = η⁶-hexamethylbenzene): Mechanistic consideration on transfer hydrogenation with bifunctional [RuCl ₂(hmb)]₂/2-aminoethanethiol catalyst system', Organometallics, vol. 29, no. 20, pp. 4584-4592. https://doi.org/10.1021/om100773a

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title = "Synthesis and reactivity of 2-aminoethanethiolato-bridged dinuclear Ru(hmb) complexes (hmb = η6-hexamethylbenzene): Mechanistic consideration on transfer hydrogenation with bifunctional [RuCl 2(hmb)]2/2-aminoethanethiol catalyst system",

abstract = "A series of dinuclear Ru(hmb) complexes with a bridging 2-aminoethanethiolato ligand (S-NH) have been newly prepared by controlling the stoichiometry of starting materials. Their catalytic performance in the racemization of an optically pure secondary alcohol indicated that the relative proportion of the Ru(hmb) and the S-NH unit in these catalyst precursors in addition to the amount of base as an activating agent is crucially important to generate a catalytically active species. Moreover, chiral versions of dinuclear Ru(S-NH)(hmb) complexes displayed excellent catalytic performance in terms of reactivity and enantioselectivity for the asymmetric transfer hydrogenation of aromatic ketones using HCO2H-N(C2H5) 3. In agreement with these results, the crossover experiment using a symmetrically bridged dinuclear complex, [Ru(μ-SCH2CH 2NH2)(hmb)]2Cl2, and its Cp*Ir dinuclear congener, [Cp*Ir(μ-SCH2CH2NH 2)]2Cl2 (Cp* = η5-C 5(CH3)5), suggested that the catalytic performance in the hydrogen transfer is originated from the mononuclear amido complex Ru(SCH2CH2NH)(hmb) bearing a Ru/NH bifunctionality.",

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AB - A series of dinuclear Ru(hmb) complexes with a bridging 2-aminoethanethiolato ligand (S-NH) have been newly prepared by controlling the stoichiometry of starting materials. Their catalytic performance in the racemization of an optically pure secondary alcohol indicated that the relative proportion of the Ru(hmb) and the S-NH unit in these catalyst precursors in addition to the amount of base as an activating agent is crucially important to generate a catalytically active species. Moreover, chiral versions of dinuclear Ru(S-NH)(hmb) complexes displayed excellent catalytic performance in terms of reactivity and enantioselectivity for the asymmetric transfer hydrogenation of aromatic ketones using HCO2H-N(C2H5) 3. In agreement with these results, the crossover experiment using a symmetrically bridged dinuclear complex, [Ru(μ-SCH2CH 2NH2)(hmb)]2Cl2, and its Cp*Ir dinuclear congener, [Cp*Ir(μ-SCH2CH2NH 2)]2Cl2 (Cp* = η5-C 5(CH3)5), suggested that the catalytic performance in the hydrogen transfer is originated from the mononuclear amido complex Ru(SCH2CH2NH)(hmb) bearing a Ru/NH bifunctionality.

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