Arene−Ruthenium Complexes of an Acyclic Thiolate−Thioether and Tridentate Thioether Derivatives Resulting from Ring-Closure Reactions
The reaction of [(η6-arene)RuCl2]2 (arene = C6Me6, 1,4-MeC6H4CHMe2) with a large excess of the dianion of bis(2-mercaptoethyl) sulfide, (HSCH2CH2)2S, obtained from deprotonation of the dithiol with freshly prepared NaOMe, gives the deep red, monomeric complexes [(η6-arene)Ru(η3-C4H8S3)] (arene = C6M...
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Published in | Inorganic chemistry Vol. 42; no. 1; pp. 96 - 106 |
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Main Authors | , , , , , , , |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
13.01.2003
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Online Access | Get full text |
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Summary: | The reaction of [(η6-arene)RuCl2]2 (arene = C6Me6, 1,4-MeC6H4CHMe2) with a large excess of the dianion of bis(2-mercaptoethyl) sulfide, (HSCH2CH2)2S, obtained from deprotonation of the dithiol with freshly prepared NaOMe, gives the deep red, monomeric complexes [(η6-arene)Ru(η3-C4H8S3)] (arene = C6Me6 (5), 1,4-MeC6H4CHMe2 (6)) in which the dianion is bound to the metal atom through one thioether and two thiolate sulfur atoms. Complex 5 reacts with [(η6-C6Me6)RuCl2]2 (4) in a 2:1 mole ratio to give a quantitative yield of the chloride salt of a binuclear cation [{(η6-C6Me6)Ru}2Cl(μ2-η2:η3-C4H8S3)]+ (7) in which the thiolate sulfur atoms of the [(η6-C6Me6)Ru(η3-C4H8S3)] group bridge to a (η6-C6Me6)RuCl unit. This compound is also obtained directly from the reaction of 4 with the dithiolate, if the Ru dimer is used in large excess. The binuclear complex [{(η6-C6Me6)Ru}2(MeCN)(μ2-η2:η3-C4H8S3)](PF6)2·MeCN, (9)(PF6)2·MeCN, is obtained by treatment of (7)Cl with NH4PF6 in acetonitrile. Protonation of 5 with HCl gave the mono- and diprotonated derivatives viz. [(η6-C6Me6)Ru(η3-C4H9S3)]Cl, (8)Cl, and [(η6-C6Me6)Ru(η3-C4H10S3)]Cl2, (10)Cl2, respectively. The reaction of 5 with methyl iodide gives both the mono- and di-S-methylated derivatives. Treatment of 5 with dibromoalkanes, Br(CH2) n Br (n = 1−5), effects ring closure to give the (η6-C6Me6)Ru dications containing the trithia mesocyclic zS3 (z = 8−12) ligands, isolated as their PF6 salts. The X-ray crystal structures of 5, 6, the solvates of (7)Cl and (9)(PF6)2, and the trithia mesocyclic Ru complexes (η6-C6Me6)Ru(zS3)(PF6)2 (z = 8−11) are reported. |
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Bibliography: | istex:9A782514B077B66A504AD4FEA8770C242B10F566 ark:/67375/TPS-JDJMRMG4-8 ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 0020-1669 1520-510X |
DOI: | 10.1021/ic0203419 |