Base-Induced Dehydrogenation of Ruthenium Hydrazine Complexes

Leslie D. Field*†, Hsiu L. Li†, Scott J. Dalgarno‡, and Ruaraidh D. McIntosh‡

† School of Chemistry, University of New South Wales, NSW 2052, Australia

‡ School of EPS-Chemistry, Heriot-Watt University, Edinburgh, Scotland, UK EH14 4AS

Inorg. Chem., 2013, 52 (3), pp 1570–1583

DOI: 10.1021/ic302449n

Publication Date (Web): January 22, 2013

Copyright © 2013 American Chemical Society

*E-mail: [email protected].

Synopsis

A series of side-on bound hydrazine, phenylhydrazine, and methylhydrazine complexes have been synthesized on Ru containing the tripodal phosphine ligand PP3iPr while the analogous complexes with PP3Ph contain end-on bound hydrazine ligands. Base treatment of the hydrazine complexes afforded a range of products including the dinitrogen and dihydride complexes as well as a hydrido ruthenaindazole complex and a hydrido methylenehydrazide complex.

Thanks Christopher. Do you have any other references where heat can induce hydrogen liberation?

Several years ago I published a work in which thermal decomposition of tosilidrazino nitriles it had evolution of H2 and N2 to form nitriles.

Nitriles from ketones: a new reaction of Tosylhydrazones.

Chem. and Ind., London , 213, (1972), England.

Yes, ligands containing acidic site such as an amide may liberate a proton upon coordination to metal moieties, This is consistent with the comment made by Christopher Jobdevairakkam in which hydrazonic ligands that include hydrazine, hydrazine, etc. may assist in liberating H2 from metal complexes. Also note coordinated ligands with beta-hydrogen may assist in the formation of H2 in certain cases in the presence of other coordinated hydrides. 

Thank you for your suggestion. If a hydrazine derivative is attached to the metal center. Is it possible that the two closely spaced hydrogen atoms are removed from hydrazine moiety leads to the conversion of hydrazine to azo?

Dear Professor Gino, Thank you for your help. Could you please send me your reference article. I do not have access to that paper. I will be happy to read that article.

Direct Synthesis of Amides from Alcohols and Amines with Liberation of H₂

Chidambaram Gunanathan, Yehoshoa Ben-David and David Milstein

Science

New Series, Vol. 317, No. 5839 (Aug. 10, 2007), pp. 790-792

Cobalt and Nickel Diimine-Dioxime Complexes as Molecular Electrocatalysts for Hydrogen Evolution with Low Overvoltages

Pierre-André Jacques, Vincent Artero, Jacques Pécaut, Marc Fontecave and Jean-Marie P. Lehn

Proceedings of the National Academy of Sciences of the United States of America

Vol. 106, No. 49 (Dec. 8, 2009), pp. 20627-20632