Synthesis and electrochemistry of novel heteronuclear Fe–Ru bi- and quatermetallocenes, conjugatively connected by ethene and thiophene bridges

Synthesis, Electrochemical Behavior, and Self‐Assembly of Metallocene‐Functionalized Thiofluorenes

“…For the isostructural ruthenocene compounds, an irreversible oxidation event was found for the ruthenocene/ ruthenocenium redox couple at E p,ox = 0.58 (6a) and 0.53 V (6b; Figure 4). This is also typical of ruthenocenes, for example, Rc-CϵC-C 6 H 4 -C 6 H 4 -SR [R = H, C(O)Me] [31] or [Ru(η 5 -C 5 H 5 ) 2 ], [59] whereas compounds like [Ru(η 5 -C 5 H 4 PPh 2 ) 2 ] [60,61a] and [Ru(η 5 -C 5 Me 5 )(C 13 Me 8 H)] [62] show a reversible oxidation character. The supporting electrolyte and cyclopentadienyl substituents of the ruthenocene compounds may affect the redox behavior.…”

Synthesis and Some Properties of Bis(ruthenocenyl)thiophene Derivatives – Possible Spin‐Coupling in the Two‐Electron Oxidized Species of Dinuclear Ruthenocenes Bridged by Thiophene Derivatives

“…Recently, a bis(ruthenocenyl)thiophene derivative has been reported to show an interesting redox behavior. [15] Results and Discussion…”

Synthesis and some properties of binuclear ruthenocene derivatives bridged by both ethene and thiophene derivatives

“…Similarly, the reaction of 5 0 -formyl-5-iodo-2,2 0 -bithiophene with the dioxaborolane 1 gave 5 0 -formyl-5-ruthenocenyl-2,2 0 -bithiophene (9), the Wittig reaction of which led to 5 0 -(2 00 -ruthenocenyl-E-ethenyl)-5-ruthenocenyl-2,2 0 -bithiophene (10) in 62% yield, along with a trace amount of its Z-isomer. The Wittig reaction of 4-ruthenocenylbenzaldehyde, which was prepared from the Suzuki reaction between 4-bromobenzaldehyde and the dioxaborolane 1, with the phosphonium salt 4 and LDA led to 4-(2 0 -ruthenocenyl-E-ethenyl)-1-ruthenocenylbenzene (11) in moderate yield.…”

“…Among aromatic linkers, benzene or naphthalene derivatives were ineffective for the spin-coupling interaction between the two ruthenocenyl sites in the two-electron oxidized species of binuclear ruthenocenes [9], but thiophene derivatives were much effective candidates [10]. Recently, a good reversibility of the ruthenocene oxidation in the analogous complex was reported [11]. These findings stimulate us to study which of an ethene or an aromatic linker can contribute strongly to the spin-coupling in the binuclear ruthenocenes containing both an ethene and thiophene derivatives in the bridge.…”