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Spectroscopy and Electrochemistry of mer-[RuCl_3(dmso)(tmen)]. Dimethylsulfoxide Is Sulfur-Bonded to Ru(II), Ru(III), and Ru(IV)

Rack, Jeffrey J. and Gray, Harry B. (1999) Spectroscopy and Electrochemistry of mer-[RuCl_3(dmso)(tmen)]. Dimethylsulfoxide Is Sulfur-Bonded to Ru(II), Ru(III), and Ru(IV). Inorganic Chemistry, 38 (1). pp. 2-3. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20180525-135926367

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Abstract

The discovery that halo−ruthenium(sulfoxide) complexes exhibit anticancer activity has stimulated interest in the nature of bonding of metal ions to dimethylsulfoxide (dmso). Both M−S and M−O bonds are observed in metal complexes containing dmso, with the former mode prevalent with “soft” metal centers. The importance of dπ-S back-bonding in S-bonded complexes has been addressed by several investigators. Especially revealing was the finding by Taube and co-workers that S to O linkage isomerism can be induced by oxidation of pentaammineruthenium(II) to ruthenium(III), thereby suggesting that dπ-S bonding is a stabilizing factor only in the lower oxidation state. However, the observation that other Ru(III)(chloro)(dmso) complexes are S-bonded led Alessio and Calligaris to propose a role for dπ-S bonding in Ru(III) as well. In the course of our work on a related complex, mer-[RuCl_3(dmso)(tmen)] (dmso is dimethylsulfoxide; tmen is N,N,N‘,N‘-tetramethylethylenediamine), we have found that dmso also can be S-bonded to Ru(IV). Our findings suggest that S(dmso) σ-donation to Ru is extensive in the Ru(III) and Ru(IV) states.


Item Type:Article
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URLURL TypeDescription
https://dx.doi.org/10.1021/ic981029vDOIArticle
https://pubs.acs.org/doi/suppl/10.1021/ic981029vPublisherSupporting Information
ORCID:
AuthorORCID
Gray, Harry B.0000-0002-7937-7876
Alternate Title:Spectroscopy and Electrochemistry of mer-[RuCl3(dmso)(tmen)]. Dimethylsulfoxide Is Sulfur-Bonded to Ru(II), Ru(III), and Ru(IV)
Additional Information:© 1999 American Chemical Society. Received August 25, 1998. We thank Mike Day, Larry Henling, Akif Tezcan, and Jay Winkler for experimental assistance and helpful discussions. This work was supported by ARO (DAAH04-95-1-0125), NSF, and NIST (ATP) Award 70NANB5H1031.
Funders:
Funding AgencyGrant Number
Army Research Office (ARO)DAAH04-95-1-0125
NSFUNSPECIFIED
National Institute of Standards and Technology (NIST)70NANB5H1031
Issue or Number:1
Record Number:CaltechAUTHORS:20180525-135926367
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180525-135926367
Official Citation:Spectroscopy and Electrochemistry of mer-[RuCl3(dmso)(tmen)]. Dimethylsulfoxide Is Sulfur-Bonded to Ru(II), Ru(III), and Ru(IV) Jeffrey J. Rack and Harry B. Gray Inorganic Chemistry 1999 38 (1), 2-3 DOI: 10.1021/ic981029v
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86638
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:25 May 2018 21:09
Last Modified:22 Nov 2019 09:58

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