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https://doi.org/10.1021/om034189+
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dc.title | Syntheses and x-ray crystal structures of di- and trinuclear trithiolate-thioether-bridged complexes of ruthenium. Electrochemistry of mixed-valence triruthenium complexes | |
dc.contributor.author | Shin, R.Y.C. | |
dc.contributor.author | Ng, S.Y. | |
dc.contributor.author | Tan, G.K. | |
dc.contributor.author | Koh, L.L. | |
dc.contributor.author | Khoo, S.B. | |
dc.contributor.author | Goh, L.Y. | |
dc.contributor.author | Webster, R.D. | |
dc.date.accessioned | 2014-10-16T08:42:49Z | |
dc.date.available | 2014-10-16T08:42:49Z | |
dc.date.issued | 2004-02-02 | |
dc.identifier.citation | Shin, R.Y.C., Ng, S.Y., Tan, G.K., Koh, L.L., Khoo, S.B., Goh, L.Y., Webster, R.D. (2004-02-02). Syntheses and x-ray crystal structures of di- and trinuclear trithiolate-thioether-bridged complexes of ruthenium. Electrochemistry of mixed-valence triruthenium complexes. Organometallics 23 (3) : 547-558. ScholarBank@NUS Repository. https://doi.org/10.1021/om034189+ | |
dc.identifier.issn | 02767333 | |
dc.identifier.uri | http://scholarbank.nus.edu.sg/handle/10635/95015 | |
dc.description.abstract | The reaction of [(HMB)RuII(κ3SSS′-tpdt)] (1; HMB = η6-C6Me6; tpdt = S(CH2CH2S-)2) with 0.5 molar equiv of [Cp*RuIIICl2]2 (2A; Cp* = η5-C5Me5) at ambient temperature gives a mixture of products consisting of the dinuclear complex [{RuIII(μ-1κ3SSS′:2κ2SS-tp dt) Cl2(CH3-CN)}Cp*RuIIICl] (6; 7%) and trinuclear complexes [{(HMB)RuII(μ3-1κ3SSS′:2κS :3κS-tpdt)}- {Cp*RuII(μ-Cl)}2] (7; 13%) and [{(HMB)RuII(μ-1κ3SSS′:2κ2S S-tpdt)} RuIIICl(μ-2κ3SSS′:3κ2SS-tp dt){Cp*RuIIICl}]Cl (8; 54%). 1 reacts with 1 molar (monomer) equiv of [RuII(COD)Cl2]n at 80°C to give yellow solids of [(HMB)RuII(μ-1κ3SSS′:2κ2 SS-tpdt)RuII(COD) Cl2] (10) in 60% yield. [Cp*RuIII(κ3SSS′-tpdt)] (2) reacts with [RuII(COD)Cl2]n in refluxing acetonitrile or with (PPh3)3RuIICl2 in MeOH at room temperature to give the dark green trinuclear complex [{Cp*RuIII(μ-1κ3SSS′: 2κ2SS-tpdt)}2RuIICl]Cl (12) in high yield. Treatment of 8, 10, and 12 with NH4PF6 in acetonitrile results in facile replacement of one or two chloro ligands with solvent molecules, giving PF6 - salts of the chloro-bridged species [{(HMB)RuII(μ-1κ3SSS′: 2κ2SS-tpdt)}RuIII(μ-2κ3 SSS′:3κ2SS-tpdt){Cp*RuIII(μ-Cl)}] (PF6)2 (9), the bis(acetonitrile) derivative [(HMB)RuII(μ-1κ3SSS′:2κ2 SS-tpdt)RuII(COD)(CH3CN)2] (PF6)2 (11), and the mono(acetonitrile) derivative [{Cp*RuIII(μ-1κ3SSS′: 2κ2SS-tpdt)}2RuII(CH3CN)] (PF6)2 (13), respectively. The triruthenium complexes can be electrochemically reduced and oxidized in one and sometimes two successive one-electron steps, with many of the reduced and oxidized species being stable on the cyclic voltammetric time scale at low temperatures (-40°C) in CH2Cl2. The location of the redox-active sites and the extent of delocalization in the species with unpaired electrons are discussed. The X-ray crystal structures of 6 and 7 and the PF6 - salts of 9, 11, and 13 are reported. The molecular structure of 7 exhibits a new μ3-1κ3SSS′:2κS: 3κS-bonding mode for the tpdt ligand. | |
dc.description.uri | http://libproxy1.nus.edu.sg/login?url=http://dx.doi.org/10.1021/om034189+ | |
dc.source | Scopus | |
dc.type | Article | |
dc.contributor.department | CHEMISTRY | |
dc.description.doi | 10.1021/om034189+ | |
dc.description.sourcetitle | Organometallics | |
dc.description.volume | 23 | |
dc.description.issue | 3 | |
dc.description.page | 547-558 | |
dc.description.coden | ORGND | |
dc.identifier.isiut | 000188533800035 | |
Appears in Collections: | Staff Publications |
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