Chemical Redox Agents for Organometallic Chemistry

A six-carbon 10π-electron aromatic system supported by group 3 metals

“…We have recently reported that 1,1 0 -ferrocenediamides 20 can support group 3 metal complexes of fused arenes 21 and have since focused on expanding this chemistry to non-fused benzenoid derivatives. Biphenyl was chosen because the two phenyl rings are only weakly conjugated 22 and it has a more accessible reduction potential than benzene ([biphenyl] 0/ À at À 2.69 V, [benzene] 0/ À at À 3.42 V and [naphthalene] 0/ À at À 2.50 V; these values are versus SCE and were calculated according to references) 23,24 . Addition of potassium graphite (KC 8 ) to a premixed tetrahydrofuran (THF) solution of (NN fc )YI(THF) 2 (1-Y, NN fc ¼ fc(NSi t BuMe 2 ) 2 , fc ¼ 1,1 0 -ferrocenediyl) and biphenyl at À 78°C led to a dark purple solution upon warming to room temperature (Fig.…”

Organization of spin- and redox-labile metal centers into Langmuir and Langmuir–Blodgett films

“…Thus, stirring a solution of 25 5 in THF in the presence of AgNO 3 gave the corresponding nitrate salts 6 in excellent yields. The new iron(III) complexes 7e-g were synthesized analogously to the previously reported alkyl functionalized complexes 7a-d. 15 While the paramagnetic nature of the iron complexes 7 30 precluded NMR investigations, the corresponding cobalt complexes were diamagnetic. The NMR spectra of complexes downfield upon cobalt coordination.…”

“…Langmuir films at the air-water interface were investigated for 30 all complexes 7 and for selected cobalt complexes. Representative pressure-area isotherms and stability plots of the films are shown in Figure 4.…”

“…25 Hierarchical self-assembly, 4 that is, supramolecular organization that is controlled in at least one dimension by stepwise growth, constitutes a useful concept for achieving cooperativity. 5 In order to effectively allow for tailoring structure and function independently, this concept requires a 30 proper separation of structurally directing elements from active sites such as spin crossover centers. 6 A major advantage of this concept then consists of the possibility to extrapolate structural trends to other functional entities.…”

Ferrocene‐ and Biferrocene‐Containing Macrocycles towards Single‐Molecule Electronics

“…[a] Conditions: scan rate v =0.04 V s −1 ; working electrode: glassy carbon; counter and reference electrode: Pt wire; all potentials reported in V relative to an internal [Cp* 2 Fe]/[Cp* 2 Fe] + standard (vs. [Cp 2 Fe]/[Cp 2 Fe] + )30 and corrected for i R s .…”