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• W2023128186 endingPage "2292" @default.
• W2023128186 startingPage "2282" @default.
• W2023128186 abstract "Abstract The monoynes [Rc*CCRc*] and [Rc′CCRc′] were obtained in improved yields using [Mo(CO) 6 ]/2‐FC 6 H 5 OH as a catalyst in the alkyne metathesis of [Rc*CCMe] and [Rc′CCMe], respectively (Rc=ruthenocenyl, Rc*=1′′,2′′,3′′,4′′,5′′‐pentamethylruthenocenyl, and Rc′=2′,3′,4′,5′‐tetramethylruthenocenyl groups). The diynes [Rc*(CC) 2 Rc*] and [Rc′(CC) 2 Rc′] were synthesized by the oxidative coupling of the corresponding terminal ethynes in good yields. The triyne [Rc*(CC) 3 Rc*] and the tetrayne [Rc*(CC) 4 Rc*] were prepared by the hetero‐ and homocoupling of [Rc*CCCCH], which was obtained from the reaction of [Rc*CCCHO] with Li[N 2 CSiMe 3 ], respectively. Although the oxidation waves did not always exhibit a clear two‐electron oxidation process, the oxidation potentials shifted to a lower potential with an increase in the number of methyl substituents on the ruthenocenyl ring, and shifted to a higher potential with the increase in the number of CC units; this result is in contrast to that found in the [Rc(CHCH) n Rc] series. The chemical oxidation of [Rc′CCRc′] yielded a stable two‐electron‐oxidized species, the structure of which was confirmed by X‐ray crystallography to be [Ru 2 (μ 2 ‐ η 6 :η 6 ‐C 5 Me 4 CCC 5 Me 4 )(η‐C 5 H 5 ) 2 ](BF 4 ) 2 . Changing the substituents (Rc, Rc*, and Rc′) had no effect on the chemical oxidation, but in the case of the Rc′ series the Me substituent increased the stability of the two‐electron‐oxidized species in solution. The diyne [Rc*(CC) 2 Rc*] and the triyne [Rc*(CC) 3 Rc*] also gave a similar but unstable two‐electron‐oxidized species. In acetone or acetonitrile, the two‐electron‐oxidized species of [Rc*CCRc*] and [Rc*(CC) 2 Rc*] gradually formed the corresponding bis(fulvene)‐type complexes. This implies that the two‐electron‐oxidized species of [Rc*(CC) n Rc*] are destabilized with the increasing n ." @default.
• W2023128186 created "2016-06-24" @default.
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• W2023128186 creator A5078634182 @default.
• W2023128186 date "2006-02-21" @default.
• W2023128186 modified "2023-10-17" @default.
• W2023128186 title "Synthesis and Some Properties of Binuclear Ruthenocenes Bridged by Oligoynes: Formation of Bis(cyclopentadienylidene)cumulene Diruthenium Complexes in the Two-Electron Oxidation" @default.
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