2,3‐Diferrocenylcyclopropenone: Synthesis, Structure, and Some Chemical and Electrochemical Properties

Abstract

Alkylation of ferrocene with tetrachlorocyclopropene in the presence of AlCl 3 followed by aqueous workup affords 2,3-diferrocenylcyclopropenone in high yield. We have studied some of this ketone's chemical transformations and electrochemical properties. 2,3-Diferrocenylcyclopropenone withstands thermolysis; it is stable in an acidic medium; the action of tetrafluoroboric acid−diethyl ether results in the formation of diferrocenyl(hydroxy)cyclopropenylium tetrafluoroborate; nucleophiles, including methyllithium and lithium aluminum

Diferrocenyl(methylthio)cyclopropenylium Iodide in the Synthesis of2,3‐Diferrocenyl‐1‐methylthio‐1,3‐dienes and ‐1,3,5‐trienes

“…Thus, the strained ring of diferrocenyl(methylthio)cyclopropenylium iodide is also readily opened when treated with [D 3 ]methyllithium. Quenching of the reaction mixture with H 2 O resulted in compounds 9-D and 10-D (Ϸ1:1) with about 92 % deuterium, as judged by 1 H NMR data (Scheme 10). The reactions described in this study will be, in our opinion, of interest to synthetic organic chemists looking to access functionalized ferrocenylpolyenes.…”

“…[1,3] Ethoxy(diferrocenyl)cyclopropenylium Tetrafluoroborate (2): Triethyloxonium tetrafluoroborate (1.0 m solution in dichloromethane, 5 mmol) was added with stirring to a solution of diferrocenylcyclopropenone (1) (0.85 g, 2 mmol) in dichloromethane (50 mL) in a dry inert atmosphere. Stirring was continued for 2 h and dry diethyl ether (100 mL) was then added.…”

“…Previously, we reported the synthesis of 2,3-diferrocenylcyclopropenone (1) through the alkylation of ferrocene with tetrachlorocyclopropene in the presence of AlCl 3 [1] and its subsequent transformation into the diferrocenyl(ethoxy)cyclopropenylium cation (2) under the action of triethyloxonium tetrafluoroborate [2,3] (Scheme 1). In the reactions of cyclopropenone 1 with RLi, diferrocenylallylic alcohols 3 were the main three-carbon ringopened products, [1] whereas diferrocenyl ketones 4 together with small amounts of 3,3-dialkyl-1,2-diferrocenylcyclopropenes 5 were obtained from reactions with RMgX [4,5] (Scheme 2).…”

“…In the reactions of cyclopropenone 1 with RLi, diferrocenylallylic alcohols 3 were the main three-carbon ringopened products, [1] whereas diferrocenyl ketones 4 together with small amounts of 3,3-dialkyl-1,2-diferrocenylcyclopropenes 5 were obtained from reactions with RMgX [4,5] (Scheme 2).…”

“…132-133°C (ref. [2] m.p 132-133°C)] and 2,3-diferrocenyl-1-methylthio-1,3-butadiene as a mixture of two isomers 9 and 10 in an approximate 1:1 ratio (by 1 Reactions of Salt 7 with Benzylmagnesium Chloride: Following the general procedure, the reaction of salt 7 (1.18 g, 2 mmol) with BnMgCl (7.0 mL of a 1 m solution in diethyl ether) in dry benzene afforded the following reaction products: 1,2-diferrocenyl-3,3-dibenzylcyclopropene (5d) [0.23 g (20 %), orange crystals, m.p. 112-114°C (ref.…”