Ferrocenecarboselenoic Acid: Synthesis and Some Reactions1. Issue 1 (20th December 2012)

• Record Type: Journal Article
• Authors: Takahashi, Toshinori; Niyomura, Osamu; Kato, Shinzi; Ebihara, Masahiro
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 639:Issue 1(2013)
• Page Start: 108
• Page End: 114
• Publication Date: 2012-12-20
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201200369
• Languages: English
• ISSNs: 0044-2313

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The first ferrocenecarboselenoic acid was synthesized and characterized. The existence of tautomeric equilibrium between the selenol (FcCOSeH) and selenoxo forms (FcCSeOH) in polar solvents was proven by ¹H‐, ¹³C‐ and ⁷⁷Se‐NMR spectra. The selenoxo form exists predominantly in a polar solvent at low temperature below –70 °C. Treatment of this acid with lithium, sodium, and potassium hydrides and with rubidium and cesium fluorides gave the corresponding alkali metal ferrocenecarboselenoates in quantitative yields. Treatment with 4‐methylphenyl isocyanate at room temperature led to ferrocenoyl 4‐methylphenylcarbamoyl selenide FcCOSeC(O)NHC₆H₄Me‐4 in high yield. A similar reaction with phenyl isothiocyanate formed a mixture of FcCOSeC(S)NHPh and FcCOSeC(SH)=NPh in moderate to good yield. The carboselenoic acid readily reacted with piperidine to give piperidinium ferrocenecarboselenoate in good yield. Air oxidation of this selenoic acid afforded diferrocenoyl selenide as a major product along with diferrocenoyl diselenide. The structures of the selenide (FcCO)₂Se and diselenide (FcCOSe)₂ were examined by single‐crystal X‐ray analysis.</p> </abstract>