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Electronic effects of bis(acetylacetone) in ruthenium(II) and ruthenium(III) complexes

Hasegawa, Tai and Lau, T. C. and Taube, H. and Schaefer, W. P. (1991) Electronic effects of bis(acetylacetone) in ruthenium(II) and ruthenium(III) complexes. Inorganic Chemistry, 30 (14). pp. 2921-2928. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20170127-155947093

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Abstract

The compound Ph_4As[Ru(acac)_2CI_2] prepared by the reaction of RuCl_3.•H_2O with acetylacetone in 1 M aqueous KCI. The anion was shown by X-ray crystallography to have a trans configuration, and it is the first trans-bis(acetylacetone) complex to have been prepared. The compound crystallizes in the monoclinic system, in the space group P1, with a = 10.082 (2) Å, b = 13.433 (2) Å, c = 14.950 (2) Å, α = 65.03 (1)°, β = 66.71 (1)°, γ = 72.02 (2)°, V= 1663 (1) Å^3, and Z = 2. A number of trans-(acac)_2 complexes of ruthenium(II), -(III), and -(IV) were prepared from the above compound and were characterized by IR, UV-vis, and ^1H NMR spectroscopy and by cyclic voltammetry. They include trans-[Ru(acac)_2(pyrazine)_2] and trans-[Ru(acac)_2(CH_3CN)_2]. The analogous cis complexes were prepared by the reaction of the ligands pyrazine and CH_3CN with Ru(acac)_3 or by thermoisomerization of the trans species, and a comparison of chemical behavior was made. For the acetonitrile derivative, the equilibrium quotient for the isomerization of the trans species to the cis was measured as 80 at 30 °C. Isomerization is so slow for the pyrazine derivative compared to the competing decomposition that a dependable value of the equilibrium quotient could not be determined, but the indications are that the cis form is the more stable. These results, and measurements of the proton affinities of the pyrazine complexes, are rationalized on the basis that when two π-acid ligands compete for π-electron density, this competition is less severe when they are disposed cis, rather than trans, to each other. None of the observations suggest that acac^- acts significantly in a π-acid capacity. When Ru(acac)_2(CH_3OH)_2) and pyrazine, mixed in equimolar proportions, react, a very insoluble polymeric material forms. The solid is a poor conductor, but the conductance is increased by a factor as high as 10^6 when it is doped with I_2.


Item Type:Article
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URLURL TypeDescription
http://dx.doi.org/10.1021/ic00014a019DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ic00014a019PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ic00014a019PublisherSupporting Information
Additional Information:© 1991 American Chemical Society. Received January 15, 1991. Support of this work by National Science Foundation Grant CHE-8511658 and National Institutes of Health Grant GM13638-21 (Stanford), National Science Foundation Grant CHE-8219039 for the purchase of the diffractometer, and the Exxon Educational Foundation for other financial support (California Institute of Technology) is gratefully acknowledged as is the contribution of Dr. Masao Mukaida (Sophia University, Tokyo), in supplying information on the synthesis of cis-[Ru-(acac)_2Cl(H_2O)].
Funders:
Funding AgencyGrant Number
NSFCHE-8511658
NIHGM13638-21
NSFCHE-8219039
Exxon Educational FoundationUNSPECIFIED
Issue or Number:14
Record Number:CaltechAUTHORS:20170127-155947093
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170127-155947093
Official Citation:Electronic effects of bis(acetylacetone) in ruthenium(II) and ruthenium(III) complexes Tai Hasegawa, T. C. Lau, Henry Taube, and W. P. Schaefer Inorganic Chemistry 1991 30 (14), 2921-2928 DOI: 10.1021/ic00014a019
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:73799
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:30 Jan 2017 16:01
Last Modified:03 Oct 2019 16:31

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