Electron-rich, bulky PNN-type ruthenium complexes

Synthesis, characterization and catalysis of alcohol dehydrogenation

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

Research output: Contribution to journalArticle

104 Citations (Scopus)

Abstract

Reaction of the electron-rich, bulky tridentate PNN ligand (PNN = 2-di-tert-butylphosphinomethyl-6-diethylaminomethylpyridine) with Ru(PPh3)3Cl2at 65 °C resulted in formation of the mononuclear dinitrogen complex (PNN)Ru(Cl)2N21a (minor) and the N2bridged Ru(ii) dinuclear complex [(PNN)Ru(Cl)2]2(µ-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(PPh3)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)Cl23, which upon reaction with one equiv. Of AgBF4gave the cationic [(PNN)Ru(CO)Cl]BF44. The dicationic [(PNN)Ru(CO)(H2O)(acetone)](BF4)25 was obtained from 3 with 2 equiv. Of AgBF4in 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 languageEnglish
Pages (from-to)107-113
Number of pages7
JournalJournal of the Chemical Society. Dalton Transactions
Issue number1
DOIs
Publication statusPublished - Nov 6 2006

Fingerprint

Ruthenium
Dehydrogenation
Carbon Monoxide
Catalysis
Alcohols
Electrons
Acetone
Argon
X ray crystallography
Ketones
Hydrogen
Esters
Gases
Ligands

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Electron-rich, bulky PNN-type ruthenium complexes : Synthesis, characterization and catalysis of alcohol dehydrogenation. / Zhang, Jing; Gandelman, Mark; Shimon, Linda J.W.; Milstein, David.

In: Journal of the Chemical Society. Dalton Transactions, No. 1, 06.11.2006, p. 107-113.

Research output: Contribution to journalArticle

@article{5ae766c6d5064d09a7eac9ac536cf8f3,
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(PPh3)3Cl2at 65 °C resulted in formation of the mononuclear dinitrogen complex (PNN)Ru(Cl)2N21a (minor) and the N2bridged Ru(ii) dinuclear complex [(PNN)Ru(Cl)2]2(µ-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(PPh3)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)Cl23, which upon reaction with one equiv. Of AgBF4gave the cationic [(PNN)Ru(CO)Cl]BF44. The dicationic [(PNN)Ru(CO)(H2O)(acetone)](BF4)25 was obtained from 3 with 2 equiv. Of AgBF4in 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 = "2006",
month = "11",
day = "6",
doi = "10.1039/b613438f",
language = "English",
pages = "107--113",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "1",

}

TY - JOUR

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 - 2006/11/6

Y1 - 2006/11/6

N2 - Reaction of the electron-rich, bulky tridentate PNN ligand (PNN = 2-di-tert-butylphosphinomethyl-6-diethylaminomethylpyridine) with Ru(PPh3)3Cl2at 65 °C resulted in formation of the mononuclear dinitrogen complex (PNN)Ru(Cl)2N21a (minor) and the N2bridged Ru(ii) dinuclear complex [(PNN)Ru(Cl)2]2(µ-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(PPh3)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)Cl23, which upon reaction with one equiv. Of AgBF4gave the cationic [(PNN)Ru(CO)Cl]BF44. The dicationic [(PNN)Ru(CO)(H2O)(acetone)](BF4)25 was obtained from 3 with 2 equiv. Of AgBF4in 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(PPh3)3Cl2at 65 °C resulted in formation of the mononuclear dinitrogen complex (PNN)Ru(Cl)2N21a (minor) and the N2bridged Ru(ii) dinuclear complex [(PNN)Ru(Cl)2]2(µ-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(PPh3)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)Cl23, which upon reaction with one equiv. Of AgBF4gave the cationic [(PNN)Ru(CO)Cl]BF44. The dicationic [(PNN)Ru(CO)(H2O)(acetone)](BF4)25 was obtained from 3 with 2 equiv. Of AgBF4in 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.

UR - http://www.scopus.com/inward/record.url?scp=84969431270&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84969431270&partnerID=8YFLogxK

U2 - 10.1039/b613438f

DO - 10.1039/b613438f

M3 - Article

SP - 107

EP - 113

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 1

ER -