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

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

doi:10.1021/om049716j

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

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

Weizmann Institute of Science

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

290 Scopus citations

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 language	English
Pages (from-to)	4026-4033
Number of pages	8
Journal	Organometallics
Volume	23
Issue number	17
DOIs	https://doi.org/10.1021/om049716j
State	Published - 16 Aug 2004
Externally published	Yes

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

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.",

author = "Jing Zhang and Mark Gandelman and Shimon, {Linda J.W.} and Haim Rozenberg and David Milstein",

year = "2004",

month = aug,

day = "16",

doi = "10.1021/om049716j",

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journal = "Organometallics",

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publisher = "American Chemical Society",

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T1 - Electron-rich, bulky ruthenium PNP-type complexes. Acceptorless catalytic alcohol dehydrogenation

AU - Zhang, Jing

AU - Gandelman, Mark

AU - Shimon, Linda J.W.

AU - Rozenberg, Haim

AU - Milstein, David

PY - 2004/8/16

Y1 - 2004/8/16

N2 - 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.

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

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