References for 4.1

Bonifacic, M.; Asmus, K.‐D.

doi:10.1007/10201365_25

Cited by 1 publication

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“…Alternatively, twice coupling of the S radical of IIB with a lone pair on the thiolate S of a second unit of the same moiety would generate simultaneously two 2c/3e S−S bonds forming species IIIC . Such (σ) 2 (σ*) 1 odd-electron bonds are a common type of bond in heteroatom-centered radicals and radical ions . The higher-energy electron in the σ* orbital of this bond will readily be transferred to the Ru centers, giving the Ru(II)−Ru(II) species 6 .…”

Section: Resultsmentioning

confidence: 99%

S-Alkylation-Induced Redox Reactions Leading to Reversible Sulfur−Sulfur Coupling in a Pentamethylcyclopentadienyl Ruthenium(III) Thiolate-Thioether System

et al. 2005

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Alkylation of [Cp*RuIII(tpdt)] (2) (Cp* = η5-C5Me5, tpdt = η3-S(CH2CH2S-)2) with MeI or Me3OBF4 resulted in the formation of a trans μ-η1-η1-S2 coupled species, [{Cp*RuII}2{μ-η6-(S(CH2)2S(CH2)2SMe)2}]2+ (3) as the predominant product. With MeI the reaction also gave a small amount of [Cp*RuII{η3-S(CH2CH2SMe)2}]I, 4(I), but in the presence of acrylonitrile (AN), the products were 4(I) and [Cp*RuII{η3-S((CH2)2S)2(CH2CHCN)}]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 I2 led to the isolation of [{Cp*RuII}2{μ-η6-(S(CH2CH2S)2)2}](I3)2, 6(I3)2, containing a cyclic RuII(μ-S2)2RuII 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*RuII}2{μ-η5-MeS(CH2)2S(CH2)2SS(CH2)2S(CH2)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*RuII{η3-MeS(CH2)2S(CH2)2SSnBu3}]+ (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*RuII{η3-S(CH2)2S(CH2)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.

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Section: Resultsmentioning

confidence: 99%