Catalytic behavior of cationic hydridoruthenium(II) complex, [RuH(NH 3)(PMe3)4]+, in H 2-hydrogenation and transfer hydrogenation of imines

Yoshihito Kayaki, Hibiki Ikeda, Jun Ichirou Tsurumaki, Isao Shimizu, Akio Yamamoto

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Abstract

Catalytic hydrogenation under H2 and transfer hydrogenation of imines by secondary alcohols with hydridoruthenium complexes bearing PMe 3 and PPh3 ligands have been examined. A cationic hydridoruthenium complex, cis-[RuH-(NH3)(PMe3) 4]PF6 (2), derived from cis-[RuH2(PMe 3)4] (1) and NH4PF6, showed higher catalytic activity for H2-hydrogenation of N-benzylideneaniline than neutral complexes such as 1 and cis- [RuClH(PMe3)4] (6). The effectiveness of cationic hydridoruthenium species for the catalytic H 2-hydrogenation of benzylideneaniline was also demonstrated by a marked increase in the yield of N-benzylaniline on treatment of 6 with AgPF 6. The cationic complex 2 was applicable to catalytic transfer hydrogenation of imines with secondary alcohols even in the absence of a base. Isotope labeling experiments using deuterated alcohols revealed that the hydrogen atom bound to the α-carbon of the donor alcohol was transferred exclusively to the imine carbon and alcoholic OD was transferred to the imine nitrogen. A rapid exchange between the alcoholic proton and the hydrido ligand of 2 was also confirmed by NMR investigation using (CH3) 2CHOD. On the basis of the experimental results the mechanisms of the H2-hydrogenation and transfer hydrogenation are discussed.

Original languageEnglish
Pages (from-to)1053-1061
Number of pages9
JournalBulletin of the Chemical Society of Japan
Volume81
Issue number9
DOIs
Publication statusPublished - 2008

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Imines
Hydrogenation
Alcohols
Bearings (structural)
Carbon
Ligands
Isotopes
Labeling
Protons
Hydrogen
Catalyst activity
Nitrogen
Nuclear magnetic resonance
Atoms

ASJC Scopus subject areas

  • Chemistry(all)

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Catalytic behavior of cationic hydridoruthenium(II) complex, [RuH(NH 3)(PMe3)4]+, in H 2-hydrogenation and transfer hydrogenation of imines. / Kayaki, Yoshihito; Ikeda, Hibiki; Tsurumaki, Jun Ichirou; Shimizu, Isao; Yamamoto, Akio.

In: Bulletin of the Chemical Society of Japan, Vol. 81, No. 9, 2008, p. 1053-1061.

Research output: Contribution to journalArticle

Kayaki, Yoshihito ; Ikeda, Hibiki ; Tsurumaki, Jun Ichirou ; Shimizu, Isao ; Yamamoto, Akio. / Catalytic behavior of cationic hydridoruthenium(II) complex, [RuH(NH 3)(PMe3)4]+, in H 2-hydrogenation and transfer hydrogenation of imines. In: Bulletin of the Chemical Society of Japan. 2008 ; Vol. 81, No. 9. pp. 1053-1061.
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abstract = "Catalytic hydrogenation under H2 and transfer hydrogenation of imines by secondary alcohols with hydridoruthenium complexes bearing PMe 3 and PPh3 ligands have been examined. A cationic hydridoruthenium complex, cis-[RuH-(NH3)(PMe3) 4]PF6 (2), derived from cis-[RuH2(PMe 3)4] (1) and NH4PF6, showed higher catalytic activity for H2-hydrogenation of N-benzylideneaniline than neutral complexes such as 1 and cis- [RuClH(PMe3)4] (6). The effectiveness of cationic hydridoruthenium species for the catalytic H 2-hydrogenation of benzylideneaniline was also demonstrated by a marked increase in the yield of N-benzylaniline on treatment of 6 with AgPF 6. The cationic complex 2 was applicable to catalytic transfer hydrogenation of imines with secondary alcohols even in the absence of a base. Isotope labeling experiments using deuterated alcohols revealed that the hydrogen atom bound to the α-carbon of the donor alcohol was transferred exclusively to the imine carbon and alcoholic OD was transferred to the imine nitrogen. A rapid exchange between the alcoholic proton and the hydrido ligand of 2 was also confirmed by NMR investigation using (CH3) 2CHOD. On the basis of the experimental results the mechanisms of the H2-hydrogenation and transfer hydrogenation are discussed.",
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