Synthetic, structural, electrochemical and electronic characterisation of heterobimetallic bis(acetylide) ferrocene complexes

Multistate Redox‐Active Metalated Triarylamines

“…The CV of the linear Fe-Ru alkynyl complex 4 is consistent with the sequential loss of three electrons in distinct, fully reversible oxidation steps with E°c entered at 0.19, 0.56, and 0.93 V (Figure 4a). By analogy with oxidation processes at the constituent "building blocks," the wave at the lowest potential can be assigned to oxidation of the electron-rich ferrocenyl unit, [20,21] whereas that at 0.56 V corresponds to the Ru II/III process; the shift to significantly higher potential than 3 reflects the decreased electron density around the ruthenium atom following the preceding oxidation at the iron center. Compared to ethynylferrocene (+0.76 V), there is a cathodic shift in the potential associated with the oxidation of the iron center due to the electron-donating properties of the [Ru(dppe) 2 ] center [a Hammett σ p electronic substituent parameter (ESP) of -0.34 Ϯ 0.04 was previously obtained from analysis of the 19 F NMR spectra].…”

Octahedral hexanuclear silver(I) and copper(I) ferrocenylacetylide complexes

“…The octahedral hexanuclear acetylide complexes with M 2 M 0 4 (M ¼ Pt, Ir; M 0 ¼ Cu, Ag) cluster cores are usually linked by the alkyl or aryl acetylides in l-g 1 ,g 2 (r,p)-coordination mode. In no cases, the octahedral cluster cores are capped by l 3 -g 1 -coordinated acetylides.Ethynylferrocene (HCBCFc) is redox-active and versatile in design of donor-metal-acceptor (D-M-A) compounds with electron transfer properties [7][8][9][10][11][12][13][14][15][16]. The metal cluster complexes of ferrocenylacetylide, however, have been unexplored comparatively [17,18].…”

Substituent and Solvent Effects on the Electrochemical Properties and Intervalence Transfer in Asymmetric Mixed‐Valent Complexes Consisting of Cyclometalated Ruthenium and Ferrocene

“…In addition to symmetric structures, [2,7] redox asymmetric systems have also been well studied, as demonstrated by the early works of the groups of Taube, [8] Henry, [9] Sato, [10] Meyer, [11] and Long, [12] as well as more recent works by Kaim, [13] Low, [14] Yuan, [15] Liu, [16] van Koten, [17] Veciana, [18] Winter, [19] and Zhong, [20] among others. [21] However, studies on the changes of E op by a combined method of structure modification and solvent variation are limited.…”