Synthesis of New [1⁴]Metallocenophanes

Abstract

Vilsmeier formylation of the trimetallic species {(C 5 Me 4 H)Fe(C 5 Me 4 )CH 2 C 5 H 4 } 2 Fe (1) gives {(C 5 Me 4 CHO)Fe(C 5 Me 4 )CH 2 C 5 H 4 } 2 Fe (2) and a triformylated product 3, the structure of which has been established by a 1 H: 1 H NOESY experiment. 2 can be converted, by three additional steps, to the new [1 4 ]ferrocenophane, (C 5 H 4 CH 2 C 5 Me 4 ) 4 Fe 4 (8), in which ferrocene and permethylated ferrocene units alternate. The methodology also permits the synthesis of heteronuclear species comprising two permethylated ferrocenylene units, a ferrocenylene unit, and a heterometallocenylene; thus, {(C 5 H 4 CH 2 C 5 Me 4 ) 4 Fe 3 Co} + PF 6 -(10) has been characterized.

Metal−Metal Interactions in Linked Metallocenes

“…We have isolated the triiron cobalt species shown in Figure 10d (M ) Co) and its tetrairon analogue (Figure 10d, M ) Fe). 193 Despite the potentially interesting metal-metal interactions possible in [1 n ]metallocenophanes, few studies in these areas have been carried out. The electrochemistry of our tetrairon species (Figure 10d, M ) Fe) shows two waves corresponding to successive oxidation of methylated and nonmethylated metallocenes.…”

Ferrocenyl- and octamethylferrocenyl-substituted phenylenevinylene-, thienylenevinylene-, and 1,1′-ferrocenylenevinylene spaced ethynes: Synthesis, metathesis polymerization, and polymer properties

“…The convenience and versatility of the formylation-post-derivatization chemistry of unsubstituted [1][2][3][4][5][6][7][8][9], aminomethylated [10][11][12][13], and even polymethylated ferrocenes [14][15][16][17][18][19][20] predestinates such compounds as ideal candidates for the design of monomers. The respective polymer matrices bear chemically reversible electrophores and offer a wide application potential in materials science such as sensor technology [21,22], polyelectrolytes, ion exchangers, electron reservoirs, organic magnets and semiconductors, as well as photonic and NLO-active materials [22,23].…”

Silicon-bridged bis(cyclohexadienyl) iron complexes: the first structurally characterised [14]ferrocenophaneElectronic supplementary information (ESI) available: experimental details and NMR spectroscopic data. See http://www.rsc.org/suppdata/cc/b1/b107874g/

“…11,12 The third product that can be isolated is the silicon-bridged cyclic tetramer {[Me 2 Si(DMCh) 2 ]Fe} 4 3 which is unprecedented in cyclopentadienyl chemistry. The CH 2 -bridged parent [1 4 ]ferrocenophane has been reported, 14,15 and we have reported the synthesis of a partially methylated analogue, 16 but, to our knowledge, there are no examples of structurally characterized [1 4 ]metallocenophanes. § The structure of {[Me 2 -Si(DMCh) 2 ]Fe} 4 is shown in Fig.…”