2005
DOI: 10.1016/j.jorganchem.2004.09.084
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Further reactions of some bis(vinylidene)diruthenium complexes

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Cited by 17 publications
(21 citation statements)
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“…Interestingly, the replacement of ruthenium in 1a with iron in 1b resulted in a slightly negative shift of the first anodic wave (at E 1/2 (1)) and significantly decreased comproportionation constant K c (Table ). It will be shown in the spectro-electrochemical section that the formally Fe­(II) centers in the terminal positions of 1b oxidize in a more localized fashion compared to the Ru­(II) derivative, 1a , as also encountered in the literature for related compounds. ,,, Accordingly, the two formally Fe­(II) centers in 1b communicate poorly through the twisted ethynyl–phenylene–N–phenylene–ethynyl bridge, in line with the small Δ E 1/2 (1–2) and K c values for [ 1b ] + . Consequently, it was hardly possible to record IR and UV–vis–NIR spectra of “pure” [ 1b ] + in the course of the corresponding spectro-electrochemical experiments described in the following section.…”
Section: Resultssupporting
confidence: 75%
“…Interestingly, the replacement of ruthenium in 1a with iron in 1b resulted in a slightly negative shift of the first anodic wave (at E 1/2 (1)) and significantly decreased comproportionation constant K c (Table ). It will be shown in the spectro-electrochemical section that the formally Fe­(II) centers in the terminal positions of 1b oxidize in a more localized fashion compared to the Ru­(II) derivative, 1a , as also encountered in the literature for related compounds. ,,, Accordingly, the two formally Fe­(II) centers in 1b communicate poorly through the twisted ethynyl–phenylene–N–phenylene–ethynyl bridge, in line with the small Δ E 1/2 (1–2) and K c values for [ 1b ] + . Consequently, it was hardly possible to record IR and UV–vis–NIR spectra of “pure” [ 1b ] + in the course of the corresponding spectro-electrochemical experiments described in the following section.…”
Section: Resultssupporting
confidence: 75%
“…of [FeCp 2 ]PF 6 at -78°C to yield the bimetallic bis(vinylidene), which is then readily deprotonated to form the bimetallic butadiynediyl complexes [{M(dppX)(L)} 2 (1,4-μ-CϵC-CϵC)] (Scheme 17). [112,[135][136][137][138] Scheme 17. Oxidative coupling and subsequent deprotonation to yield bimetallic μ-1,3-diyne-1,4-diyl complexes.…”
Section: Cp]mentioning
confidence: 99%
“…[136,[145][146][147] Therefore the intermediacy of vinylidenes cannot be excluded in the conversion of alkynyl radical cations into carbonyls. However, these reactions are generally slow and a growing body of evidence points to more direct hydrolysis mechanisms that may occur on faster timescales.…”
Section: Whereas Reaction Of For Example [Ru{c=c(h)-ph}l(pph 3 )Cp]mentioning
confidence: 99%
“…Similar dimerizationp henomena have previously been observed for analogousR ua nd other metal complexes. [22] In particular,t he aforementioned divinylidene [{Cp(PPh 3 ) 2 Ru} 2 -(m-C 4 Ph 2 )][PF 6 ] 2 ,i solated by Bruce et al by treatment of Cp(PPh 3 ) 2 RuC 2 Ph with AgC 2 Ph, [23] presents an analogouss tructure to that hypothesized for 2F.…”
Section: Characterizationmentioning
confidence: 95%
“…For analogous metal complexes,e xperimental observations, supported by calculations, have identified C b of the alkynyl moiety as as ite very prone to further reactivity. [21][22][23][24] Thus, one possible explanation for the chemical reaction observed here,r esulting from the oxidationo f2A,c ould be that of aC b -C b radicald imerizationb etween two oxidized [Ru*]-DHA species. Am ore detailed investigation into the oxidative dimerizationp roducts of Cp(PPh 3 [23] In othert rials, oxidations of Cp*(dppe)RuC 2 PhX using AgOTf also resulted in unstable radical cations leadingt om ore complex product mixtures.…”
Section: Characterizationmentioning
confidence: 99%