Electron-rich, bulky ruthenium PNP-type complexes. Acceptorless catalytic alcohol dehydrogenation

Jing Zhang, Mark Gandelman, Linda J W Shimon, Haim Rozenberg, David Milstein

Research output: Contribution to journalArticle

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Abstract

Reaction of the electron-rich, bulky tridentate PNP ligand (2,6-bis-(di-tert-butylphosphinomethyl)pyridine) with Ru(PPh3) 3Cl2 at 65°C resulted in formation of a solution containing the dinitrogen monomeric Ru(II) complex la and the N 2-bridged dinuclear Ru(II) complex 1b, which can be interconverted. Passing argon through the solution results in formation of pure 1b. The Ru(II) hydride dinitrogen complex 2 was obtained by the reaction of complex 1b with 2 equiv of NaBEt3H. Complex 1b reacted with 4 equiv of AgOCOCF 3 to yield [Ru(PNP)(CF3COO)2], 3. The Ru(II) carbonyl hydride complex 4 was obtained by the reaction of PNP and Ru 2(OAc)4 in methanol as a result of O-H activation and decarbonylation of methanol. Complexes 1b, 2, and 4 were structurally characterized by X-ray crystallography. Complexes 1b and 2 catalyze the dehydrogenation of secondary alcohols to the corresponding ketones with good yields and high selectivity accompanied with the evolution of dihydrogen in a homogeneous system without a need for a hydrogen acceptor. The presumed intermediate Ru dihydride complex is generated in situ by reaction 1b or 2 with a base (1 equiv for each Ru-Cl bond), and the reaction can proceed in the absence of excess base or acid.

Original languageEnglish
Pages (from-to)4026-4033
Number of pages8
JournalOrganometallics
Volume23
Issue number17
DOIs
Publication statusPublished - Aug 16 2004

Fingerprint

Ruthenium
Dehydrogenation
dehydrogenation
Hydrides
ruthenium
Methanol
alcohols
Alcohols
Electrons
Argon
X ray crystallography
Ketones
Hydrogen
electrons
Chemical activation
hydrides
Ligands
methyl alcohol
Acids
dihydrides

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Electron-rich, bulky ruthenium PNP-type complexes. Acceptorless catalytic alcohol dehydrogenation. / Zhang, Jing; Gandelman, Mark; Shimon, Linda J W; Rozenberg, Haim; Milstein, David.

In: Organometallics, Vol. 23, No. 17, 16.08.2004, p. 4026-4033.

Research output: Contribution to journalArticle

Zhang, Jing ; Gandelman, Mark ; Shimon, Linda J W ; Rozenberg, Haim ; Milstein, David. / Electron-rich, bulky ruthenium PNP-type complexes. Acceptorless catalytic alcohol dehydrogenation. In: Organometallics. 2004 ; Vol. 23, No. 17. pp. 4026-4033.
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abstract = "Reaction of the electron-rich, bulky tridentate PNP ligand (2,6-bis-(di-tert-butylphosphinomethyl)pyridine) with Ru(PPh3) 3Cl2 at 65°C resulted in formation of a solution containing the dinitrogen monomeric Ru(II) complex la and the N 2-bridged dinuclear Ru(II) complex 1b, which can be interconverted. Passing argon through the solution results in formation of pure 1b. The Ru(II) hydride dinitrogen complex 2 was obtained by the reaction of complex 1b with 2 equiv of NaBEt3H. Complex 1b reacted with 4 equiv of AgOCOCF 3 to yield [Ru(PNP)(CF3COO)2], 3. The Ru(II) carbonyl hydride complex 4 was obtained by the reaction of PNP and Ru 2(OAc)4 in methanol as a result of O-H activation and decarbonylation of methanol. Complexes 1b, 2, and 4 were structurally characterized by X-ray crystallography. Complexes 1b and 2 catalyze the dehydrogenation of secondary alcohols to the corresponding ketones with good yields and high selectivity accompanied with the evolution of dihydrogen in a homogeneous system without a need for a hydrogen acceptor. The presumed intermediate Ru dihydride complex is generated in situ by reaction 1b or 2 with a base (1 equiv for each Ru-Cl bond), and the reaction can proceed in the absence of excess base or acid.",
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