Electron-rich, bulky PNN-type ruthenium complexes: Synthesis, characterization and catalysis of alcohol dehydrogenation

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

doi:10.1039/b613438f

Electron-rich, bulky PNN-type ruthenium complexes: Synthesis, characterization and catalysis of alcohol dehydrogenation

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

Weizmann Institute of Science

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Abstract

Reaction of the electron-rich, bulky tridentate PNN ligand (PNN = 2-di-tert-butylphosphinomethyl-6-diethylaminomethylpyridine) with Ru(PPh ₃)₃Cl₂ at 65 °C resulted in formation of the mononuclear dinitrogen complex (PNN)Ru(Cl)₂N₂ 1a (minor) and the N₂ bridged Ru(ii) dinuclear complex [(PNN)Ru(Cl) ₂]₂(-N₂) 1b (major). These complexes can be interconverted; passing argon through a solution of the mixture resulted in formation of pure 1b. The cationic square-pyramidal [(PNN)Ru(PPh ₃)Cl]OTf 2 was obtained by the reaction of complex 1b with silver triflate followed by PPh₃. Reaction of complex 1b with CO yielded (PNN)Ru(CO)Cl₂ 3, which upon reaction with one equiv. of AgBF ₄ gave the cationic [(PNN)Ru(CO)Cl]BF₄ 4. The dicationic [(PNN)Ru(CO)(H₂O)(acetone)](BF₄)₂ 5 was obtained from 3 with 2 equiv. of AgBF₄ in acetone solution. Complexes 1b, 2 and 5 were structurally characterized by X-ray crystallography. Complexes 1b and 3, upon addition of an equivalent of base, catalyzed the dehydrogenation of secondary alcohols to the corresponding ketones and primary alcohols to esters in good yields and high selectivity accompanied with the evolution of hydrogen gas.

Original language	English
Pages (from-to)	107-113
Number of pages	7
Journal	Dalton Transactions
Issue number	1
DOIs	https://doi.org/10.1039/b613438f
State	Published - 2007
Externally published	Yes

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title = "Electron-rich, bulky PNN-type ruthenium complexes: Synthesis, characterization and catalysis of alcohol dehydrogenation",

abstract = "Reaction of the electron-rich, bulky tridentate PNN ligand (PNN = 2-di-tert-butylphosphinomethyl-6-diethylaminomethylpyridine) with Ru(PPh 3)3Cl2 at 65 °C resulted in formation of the mononuclear dinitrogen complex (PNN)Ru(Cl)2N2 1a (minor) and the N2 bridged Ru(ii) dinuclear complex [(PNN)Ru(Cl) 2]2(-N2) 1b (major). These complexes can be interconverted; passing argon through a solution of the mixture resulted in formation of pure 1b. The cationic square-pyramidal [(PNN)Ru(PPh 3)Cl]OTf 2 was obtained by the reaction of complex 1b with silver triflate followed by PPh3. Reaction of complex 1b with CO yielded (PNN)Ru(CO)Cl2 3, which upon reaction with one equiv. of AgBF 4 gave the cationic [(PNN)Ru(CO)Cl]BF4 4. The dicationic [(PNN)Ru(CO)(H2O)(acetone)](BF4)2 5 was obtained from 3 with 2 equiv. of AgBF4 in acetone solution. Complexes 1b, 2 and 5 were structurally characterized by X-ray crystallography. Complexes 1b and 3, upon addition of an equivalent of base, catalyzed the dehydrogenation of secondary alcohols to the corresponding ketones and primary alcohols to esters in good yields and high selectivity accompanied with the evolution of hydrogen gas.",

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

year = "2007",

doi = "10.1039/b613438f",

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pages = "107--113",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "1",

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T1 - Electron-rich, bulky PNN-type ruthenium complexes

T2 - Synthesis, characterization and catalysis of alcohol dehydrogenation

AU - Zhang, Jing

AU - Gandelman, Mark

AU - Shimon, Linda J.W.

AU - Milstein, David

PY - 2007

Y1 - 2007

N2 - Reaction of the electron-rich, bulky tridentate PNN ligand (PNN = 2-di-tert-butylphosphinomethyl-6-diethylaminomethylpyridine) with Ru(PPh 3)3Cl2 at 65 °C resulted in formation of the mononuclear dinitrogen complex (PNN)Ru(Cl)2N2 1a (minor) and the N2 bridged Ru(ii) dinuclear complex [(PNN)Ru(Cl) 2]2(-N2) 1b (major). These complexes can be interconverted; passing argon through a solution of the mixture resulted in formation of pure 1b. The cationic square-pyramidal [(PNN)Ru(PPh 3)Cl]OTf 2 was obtained by the reaction of complex 1b with silver triflate followed by PPh3. Reaction of complex 1b with CO yielded (PNN)Ru(CO)Cl2 3, which upon reaction with one equiv. of AgBF 4 gave the cationic [(PNN)Ru(CO)Cl]BF4 4. The dicationic [(PNN)Ru(CO)(H2O)(acetone)](BF4)2 5 was obtained from 3 with 2 equiv. of AgBF4 in acetone solution. Complexes 1b, 2 and 5 were structurally characterized by X-ray crystallography. Complexes 1b and 3, upon addition of an equivalent of base, catalyzed the dehydrogenation of secondary alcohols to the corresponding ketones and primary alcohols to esters in good yields and high selectivity accompanied with the evolution of hydrogen gas.

AB - Reaction of the electron-rich, bulky tridentate PNN ligand (PNN = 2-di-tert-butylphosphinomethyl-6-diethylaminomethylpyridine) with Ru(PPh 3)3Cl2 at 65 °C resulted in formation of the mononuclear dinitrogen complex (PNN)Ru(Cl)2N2 1a (minor) and the N2 bridged Ru(ii) dinuclear complex [(PNN)Ru(Cl) 2]2(-N2) 1b (major). These complexes can be interconverted; passing argon through a solution of the mixture resulted in formation of pure 1b. The cationic square-pyramidal [(PNN)Ru(PPh 3)Cl]OTf 2 was obtained by the reaction of complex 1b with silver triflate followed by PPh3. Reaction of complex 1b with CO yielded (PNN)Ru(CO)Cl2 3, which upon reaction with one equiv. of AgBF 4 gave the cationic [(PNN)Ru(CO)Cl]BF4 4. The dicationic [(PNN)Ru(CO)(H2O)(acetone)](BF4)2 5 was obtained from 3 with 2 equiv. of AgBF4 in acetone solution. Complexes 1b, 2 and 5 were structurally characterized by X-ray crystallography. Complexes 1b and 3, upon addition of an equivalent of base, catalyzed the dehydrogenation of secondary alcohols to the corresponding ketones and primary alcohols to esters in good yields and high selectivity accompanied with the evolution of hydrogen gas.

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Electron-rich, bulky PNN-type ruthenium complexes: Synthesis, characterization and catalysis of alcohol dehydrogenation

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