Intramolecular Conversions of (Aminoferrocenylpenta-14-dienyl)-ferrocenylcarbenes: Synthesis of Diferrocenylmono- bi- tricycles and Amino(diferrocenyl)hexa-135-trienes

摘要

Synthesis of 3,4-diferrocenyltoluene (>7), 1-morpholino- and 1-piperidino-2,3-diferrocenylbicyclo[3.1.0]hex-2-enes >8a, >8b, 1-morpholino- and 1-piperidino-7-ferrocenyl-3,4-ferrocenobicyclo[3.2.1]oct-6-enes >9a, >9b, 2- and 3-amino(diferrocenyl)-hexa-1,3,5-trienes >10a,>b, >11a,>b by reactions of amino(diferrocenyl)cyclopropenylium tetrafluoro-borates with 1-methylprop-2-enylmagnesium chloride at 80 °C is described. The structures of the compounds obtained were determined by IR, ¹H- and ¹³C-NMR spectroscopy and mass spectrometry. X-ray diffraction data for 1-piperidino-7-ferrocenyl-3,4-ferroceno-bicyclo[3.2.1]oct-6-ene (>9b), 2-morpholino- and 2-piperidino-1,3-diferrocenyl-4-methyl-hexa-1,3,5-trienes >10a and >10b is presented. The electrochemical behaviour of compounds >7, >8a, >10a and >10b was investigated by means of cyclic voltammetry and square wave voltammetry. For >7 and >8a two electrochemical processes (I-II), attributed to the oxidation of the ferrocene moieties were found. On the other hand for compounds >10a and >10b a single electron transfer for both ferrocene groups and the electrochemical generation of the monocation and dication species were detected.