Please use this identifier to cite or link to this item: https://doi.org/10.1021/ic0203419
Title: Arene-ruthenium complexes of an acyclic thiolate-thioether and tridentate thioether derivatives resulting from ring-closure reactions
Authors: Shin, R.Y.C.
Bennett, M.A.
Yoong Goh, L. 
Chen, W.
Hockless, D.C.R.
Leong, W.K. 
Mashima, K.
Willis, A.C.
Issue Date: Jan-2003
Citation: Shin, R.Y.C., Bennett, M.A., Yoong Goh, L., Chen, W., Hockless, D.C.R., Leong, W.K., Mashima, K., Willis, A.C. (2003-01). Arene-ruthenium complexes of an acyclic thiolate-thioether and tridentate thioether derivatives resulting from ring-closure reactions. Inorganic Chemistry 42 (1) : 96-106. ScholarBank@NUS Repository. https://doi.org/10.1021/ic0203419
Abstract: 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)Flu(η3-C4 H8S3)] (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}2 Cl(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:η3C4 H8S3)](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)nBr (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.
Source Title: Inorganic Chemistry
URI: http://scholarbank.nus.edu.sg/handle/10635/93137
ISSN: 00201669
DOI: 10.1021/ic0203419
Appears in Collections:Staff Publications

Show full item record
Files in This Item:
There are no files associated with this item.

SCOPUSTM   
Citations

37
checked on Sep 24, 2018

WEB OF SCIENCETM
Citations

35
checked on Sep 17, 2018

Page view(s)

38
checked on Sep 14, 2018

Google ScholarTM

Check

Altmetric


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.