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https://doi.org/10.1021/om049081o
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dc.title | S-alkylation-induced redox reactions leading to reversible sulfur-sulfur coupling in a pentamethylcyclopentadienyl ruthenium(III) thiolate-thioether system | |
dc.contributor.author | Shin, R.Y.C. | |
dc.contributor.author | Teo, M.E. | |
dc.contributor.author | Leong, W.K. | |
dc.contributor.author | Vittal, J.J. | |
dc.contributor.author | Yip, J.H.K. | |
dc.contributor.author | Goh, L.Y. | |
dc.contributor.author | Webster, R.D. | |
dc.date.accessioned | 2014-10-16T08:39:39Z | |
dc.date.available | 2014-10-16T08:39:39Z | |
dc.date.issued | 2005-03-28 | |
dc.identifier.citation | Shin, R.Y.C., Teo, M.E., Leong, W.K., Vittal, J.J., Yip, J.H.K., Goh, L.Y., Webster, R.D. (2005-03-28). S-alkylation-induced redox reactions leading to reversible sulfur-sulfur coupling in a pentamethylcyclopentadienyl ruthenium(III) thiolate-thioether system. Organometallics 24 (7) : 1483-1494. ScholarBank@NUS Repository. https://doi.org/10.1021/om049081o | |
dc.identifier.issn | 02767333 | |
dc.identifier.uri | http://scholarbank.nus.edu.sg/handle/10635/94750 | |
dc.description.abstract | Alkylation of [Cp*Ru III(tpdt)] (2) (Cp* = η 5-C 5Me 5, tpdt = η 3-S (CH 2CH 2S -) 2) with MeI orMe 3OBF 4 resulted in the formation of a trans μ-η 1-η 1-S 2 coupled species, [{Cp*Ru II} 2{μ-η 6-(S(CH 2) 2S(CH 2) 2SMe) 2}] 2+ (3) as the predominant product. With MeI the reaction also gave a small amount of [Cp*Ru II{η 3-S(CH 2CH 2SMe) 2}]I, 4(I), but in the presence of acrylonitrile (AN), the products were 4(I) and [Cp*Ru II{η 3-S((CH 2) 2S) 2(CH 2CHCN)}] I, 5(I), of which the latter was the sole product from the reaction of 2 with AN in the presence of iodine. 2 was electrochemically easily oxidized in a one-electron process; its chemical oxidation with I 2 led to the isolation of [{Cp*Ru II} 2{μ-η 6- (S(CH 2CH 2S) 2) 2}](I 3) 2,6(I 3) 2, containing a cyclic Ru II(μ-S 2) 2Ru II core. A combination of electrochemical, EPR, UV-vis, and NMR experiments indicated that the solution phase chemistry of 3 is governed by its facile reversible dissociation into the mononuclear cation radical (3A). Based on this phenomenon were rationalized the pathways leading to the formation of the dinuclear species [{Cp*Ru II} 2{μ-η 5-MeS(CH 2) 2-S(CH 2) 2SS(CH 2) 2S(CH 2) 2S}] + (7) from the interaction of 3 and 2, or of a mixture of 4(I) and 5(I) in the presence of MeI and AN, and of [Cp*Ru II{η 3-MeS(CH 2) 2S(CH 2) 2SSnBu 3}] + (9) from reaction with tri(n-butyl)tin hydride. Electrochemical measurements indicated that the sodium naphthalide reduction of 3 to generate the mono-S-methylated derivative, [Cp*Ru II-{η 3- S(CH 2) 2S(CH 2) 2SMe}] (8), occurred through 3A. It is proposed that some of the transformations also involved internal electron transfers and nucleophilic displacements. The X-ray crystal structures of the complexes 3-9 are reported. © 2005 American Chemical Society. | |
dc.description.uri | http://libproxy1.nus.edu.sg/login?url=http://dx.doi.org/10.1021/om049081o | |
dc.source | Scopus | |
dc.type | Article | |
dc.contributor.department | CHEMISTRY | |
dc.description.doi | 10.1021/om049081o | |
dc.description.sourcetitle | Organometallics | |
dc.description.volume | 24 | |
dc.description.issue | 7 | |
dc.description.page | 1483-1494 | |
dc.description.coden | ORGND | |
dc.identifier.isiut | 000227861100018 | |
Appears in Collections: | Staff Publications |
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