1,4-Diethynylbenzene Bridged Fe(Cp*)(dppe) Units: Mixed-Valence 35-Electron and Bisiron(III) 34-Electron Complexes

Syntheses and molecular structures of group 8 benzonitrile complexes

“…70 mV) indicates the metal centres to be essentially independent [26]. The small separation of the electrochemical events contrasts dramatically with the relatively large (DE = 260 mV, K c = 2.6 · 10 4 ) separation of the oxidation processes observed in the related 1,4-diethynyl benzene bridged species [{Fe(dppe)Cp*} 2 (l-C"CC 6 -H 4 C"C)] [27], and consequently the high thermodynamic stability of the mono-oxidised form of the bis(acetylide) complex towards disproportionation [26]. Compound 9 displayed a reversible oxidation wave at +0.73 V and a second irreversible wave (E p = +1.45 V) that resulted in the formation of a deposit on the electrode precluding further characterisation of this wave.…”

Metall‐Alkinyl‐σ‐Komplexe: Synthesen und Materialien

“…Zur Untersuchung der Elektronenleitung zwischen verbrückten Übergangsmetallzentren wurde häufig auf konjugierte, Alkinyl-verbrückte Cp*Fe(dppe)-Einheiten zurück-gegriffen. [23,[170][171][172][173][174][175] [178] Der Einfluss der Länge der konjugierten Brücke wurde anhand von Verbindungen vom Typ [Fp*-(C C) n -Fp*] (n = 1-4, 6; Fp* = h 5 -(C 5 Me 5 )Fe(CO) 2 ) untersucht. [179,180] Die oligomeren Komplexe wurden durch Cu-katalysierte oxidative Kupplung hergestellt.…”

New Access to Homodinuclear Half‐Sandwich Vinylidenemanganese Complexes

“…[3,[6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] In particular, the dinuclear transition metal acetylide complexes offer an interesting perspective for the build-up of organometallic systems as molecular-level single-electron devices and the bottom-up construction of miniaturised components capable of performing specific electronic functions. [8][9][10][11][12][13][14][15][16][17][18][19][20] Our ongoing interest in such building blocks is devoted to the synthesis and physical properties of molecular species which might function as wires.…”

“…Specifically, they should consist of an all-carbon chain capped by two redox-active metal termini. [6][7][8][9][10][11][12][13][14][15][16][17] We sought to explore reactions of dinuclear vinylidene precursor complexes which would ultimately lead to polyyne ligand containing complexes. We recently reported the chemistry and reactivity of Mn II and Mn III half-sandwich Me 2 PCH 2 CH 2 PMe 2 (dmpe) alkynyl complexes and their conversion to (vinylidene)Mn I species.…”

“…Similar types of dinuclear vinylidene complexes have been reported with terminal ends capped by various other transition metals such as Ru, [17b] Rh [27] or Fe. [7] We herein report access to new dinuclear half-sandwich complexes of the type [{Mn(MeC 5 H 4 )(R 2 PCH 2 CH 2 PR 2 ) = C=C(H)} 2 {X}] (R = Me, Et) (X = {µ-1,4-C 6 H 4 }, {µ-1,3-C 6 H 4 } and {µ-4,4-C 6 H 4 -C 6 H 4 }). It has been demonstrated by other groups that similar types of dinuclear vinylidene complexes can serve as valuable starting materials for obtaining access to dinuclear acetylide complexes.…”