C/O/P/S cycles derived from oxidative intramolecular disulfide (–S–S–) coupling of ferrocenyl dithiophosphonates

摘要: The symmetrical 2,4-diferrocenyl-1,3-dithiadiphosphetane disulfide dimer, [FcP(μ-S)S]2 (Fc = ferrocenyl), reacts with ethanediol (molar ratio 1:1), trans-1,2-cyclohexanediol 1:1) and pentaerythritol 2:1) at 70 °C to form the respective dithiophosphonic acids in high yield. were readily deprotonated by anhydrous ammonia yield corresponding ammonium salts (NH4)2[S2P(Fc)OCH2CH2O(Fc)PS2] (1), (NH4)2[(S2PFc)2(trans-1,2-O,O′-C6H10)] (2) (NH4)4[C{CH2OPS2(Fc)}4] (3). undergo facile intramolecular oxidation mild oxidant iodine a I2/MeOH mixture resulting new ferrocene-based disulfides of type [{-CH2OP(S)(Fc)S-}2] (4), [(S2P-Fc)2(trans-1,2-O,O′-C6H10)] (5) [C{CH2OP(S)(Fc)S}4] (6). compounds 1–6 characterized 1H 31P NMR bulk purity confirmed either ESI-MS or elemental analysis. Compounds 4–6 additionally single crystal X-ray analyses 4 6 subjected electrochemical investigations. represent first examples structurally S–S coupled products derived from dithiophosphonates.