Arene-Ruthenium Complexes of an Acyclic Thiolate-Thioether and Tridentate Thioether Derivatives Resulting from Ring-Closure Reactions
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- 作者：Richard Y. C. Shin ; Martin A. Bennett ; Lai Yoong Goh ; Wei Chen ; David C. R. Hockless ; Weng Kee Leong ; Kazushi Mashima ; and Anthony C. Willis
- 刊名：Inorganic Chemistry
- 出版年：2003
- 出版时间：January 13, 2003
- 年：2003
- 卷：42
- 期：1
- 页码：96 - 106
- 全文大小：261K
- 年卷期：v.42,no.1(January 13, 2003)
- ISSN：1520-510X
文摘
The reaction of [(
rs/eta.gif" BORDER=0 >6-arene)RuCl2]2 (arene = C6Me6, 1,4-MeC6H4CHMe2) with a large excess of the dianion ofbis(2-mercaptoethyl) sulfide, (HSCH2CH2)2S, obtained from deprotonation of the dithiol with freshly prepared NaOMe,gives the deep red, monomeric complexes [(rs/eta.gif" BORDER=0 >6-arene)Ru(rs/eta.gif" BORDER=0 >3-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 5reacts with [(rs/eta.gif" BORDER=0 >6-C6Me6)RuCl2]2 (4) in a 2:1 mole ratio to give a quantitative yield of the chloride salt of a binuclearcation [{(rs/eta.gif" BORDER=0 >6-C6Me6)Ru}2Cl(
r.gif">2-rs/eta.gif" BORDER=0 >2:rs/eta.gif" BORDER=0 >3-C4H8S3)]+ (7) in which the thiolate sulfur atoms of the [(rs/eta.gif" BORDER=0 >6-C6Me6)Ru(rs/eta.gif" BORDER=0 >3-C4H8S3)]group bridge to a (rs/eta.gif" BORDER=0 >6-C6Me6)RuCl unit. This compound is also obtained directly from the reaction of 4 with thedithiolate, if the Ru dimer is used in large excess. The binuclear complex [{(rs/eta.gif" BORDER=0 >6-C6Me6)Ru}2(MeCN)(r.gif">2-rs/eta.gif" BORDER=0 >2:rs/eta.gif" BORDER=0 >3-C4H8S3)](PF6)2·MeCN, (9)(PF6)2·MeCN, is obtained by treatment of (7)Cl with NH4PF6 in acetonitrile. Protonationof 5 with HCl gave the mono- and diprotonated derivatives viz. [(rs/eta.gif" BORDER=0 >6-C6Me6)Ru(rs/eta.gif" BORDER=0 >3-C4H9S3)]Cl, (8)Cl, and [(rs/eta.gif" BORDER=0 >6-C6Me6)Ru(rs/eta.gif" BORDER=0 >3-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)nBr (n = 1-5), effects ring closure to givethe (rs/eta.gif" BORDER=0 >6-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(rs/eta.gif" BORDER=0 >6-C6Me6)Ru(zS3)(PF6)2 (z = 8-11) are reported.
rs/eta.gif" BORDER=0 >6-arene)RuCl2]2 (arene = C6Me6, 1,4-MeC6H4CHMe2) with a large excess of the dianion ofbis(2-mercaptoethyl) sulfide, (HSCH2CH2)2S, obtained from deprotonation of the dithiol with freshly prepared NaOMe,gives the deep red, monomeric complexes [(rs/eta.gif" BORDER=0 >6-arene)Ru(rs/eta.gif" BORDER=0 >3-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 5reacts with [(rs/eta.gif" BORDER=0 >6-C6Me6)RuCl2]2 (4) in a 2:1 mole ratio to give a quantitative yield of the chloride salt of a binuclearcation [{(rs/eta.gif" BORDER=0 >6-C6Me6)Ru}2Cl(r.gif">2-rs/eta.gif" BORDER=0 >2:rs/eta.gif" BORDER=0 >3-C4H8S3)]+ (7) in which the thiolate sulfur atoms of the [(rs/eta.gif" BORDER=0 >6-C6Me6)Ru(rs/eta.gif" BORDER=0 >3-C4H8S3)]group bridge to a (rs/eta.gif" BORDER=0 >6-C6Me6)RuCl unit. This compound is also obtained directly from the reaction of 4 with thedithiolate, if the Ru dimer is used in large excess. The binuclear complex [{(rs/eta.gif" BORDER=0 >6-C6Me6)Ru}2(MeCN)(r.gif">2-rs/eta.gif" BORDER=0 >2:rs/eta.gif" BORDER=0 >3-C4H8S3)](PF6)2·MeCN, (9)(PF6)2·MeCN, is obtained by treatment of (7)Cl with NH4PF6 in acetonitrile. Protonationof 5 with HCl gave the mono- and diprotonated derivatives viz. [(rs/eta.gif" BORDER=0 >6-C6Me6)Ru(rs/eta.gif" BORDER=0 >3-C4H9S3)]Cl, (8)Cl, and [(rs/eta.gif" BORDER=0 >6-C6Me6)Ru(rs/eta.gif" BORDER=0 >3-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)nBr (n = 1-5), effects ring closure to givethe (rs/eta.gif" BORDER=0 >6-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(rs/eta.gif" BORDER=0 >6-C6Me6)Ru(zS3)(PF6)2 (z = 8-11) are reported.