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

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

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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
StatePublished - 6 Nov 2006
Externally publishedYes

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