Alkali Metal and Organo Group‐14 Element Ferrocenecarbo­selenoates: Synthesis and Structures

Abstract

Lithium, sodium, and potassium ferrocenecarboselenoates were synthesized in good yields by the reaction of ferrocenoyl chloride with the corresponding metal selenides. In air, the salts quickly oxidized to give diferrocenoyl diselenide. The salts readily reacted with alkyl and organo-germanium, -tin and -lead halides to give the corresponding Se-alkyl and Se-organo Group-14 element ferrocenecarboselenoates [(FcCOSe) x MPh 4-x (M = Ge, Sn, Pb; x = 1-3) in moderate to 96 good yields. In contrast, the reaction of the sodium and potassium salts with trimethylsilyl chloride led to O-trimethylsilyl ferrocenecarboselenoate FcCSeOSiMe 3 . Treatment of the O-silyl ester with RbF and CsF led to rubidium and cesium ferrocenecarboselenoates, respectively,ingoodyields.ThestructuresofFcCOSetBu,(FcCOSe) 2 SnPh 2 ,and FcCOSePbPh 3 were revealed by X-ray molecular structure analysis. synthesis of new carbochalcogenoic acid derivatives, we describe herein the synthesis of a series of alkali metal and Sealkyl and Se-organo Group-14 element ferrocenecarboselenoates, [5] along with the X-ray molecular structures of Setert-butyl ferrocenecarboselenoate, Se-diphenyltin bis(ferrocenecarboselenoate), and Se-triphenyllead ferrocenecarboselenoate. Results and Discussion Synthesis Alkali Metal FerrocenecarboselenoatesAfter we considered previous papers, [6] the reaction conditions of ferrocenoyl chloride with alkali metal selenides were examined for the synthesis of lithium (1), sodium (2), and potassium ferrocenecarboselenoate (3) (Scheme 1). As a result, the reactions of ferrocenoyl chloride with an excess of alkali metal selenide in acetonitrile were found to give the corresponding salts 1-3 in good yields. For example, ferrocenoyl chloride was added dropwise to a suspension of freshly prepared sodium selenide (1.5 mol amount) in acetonitrile, and the mixture was stirred at 0°C for 1 h. Filtration of the resulting precipitates (excess Na 2 Se and NaCl) and evaporation of the solvent under reduced pressure afforded sodium ferrocenecarboselenoate (2) in 80 % yield as orange-brown micro crystals. Under similar conditions, the reactions with lithium and potas-Scheme 1.