Novel Fluorinated Phosphorus-Sulfur Heteroatom Compounds: Synthesis and Characterization of Ferrocenyl- and Aryl-Phosphonofluorodithioic Salts, Adducts, and Esters

• Published in: Molecules (Basel, Switzerland) Vol. 20; no. 7; pp. 12175 - 12197
• Main Authors: Hua, Guoxiong, Du, Junyi, Surgenor, Brian A, Slawin, Alexandra M Z, Woollins, J Derek
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 03-07-2015; MDPI
• Subjects: 2,4-diferrocenyl-1,3,2,4-diathiadiphosphetane 2,4-disulfide; Esters; esters of phenylphosphono-fluoridodithioates; Ferrous Compounds - chemistry; Fluorides; Fluorine; Fluorine - chemistry; Metallocenes; mono- and di-halogenated alkanes; Phosphorus - chemistry; Potassium; Salts; salts of phenyldithio- fluorophosphinic acids; Sulfur - chemistry; esters of phenylphosphono-fluoridodithioates; 2,4-diferrocenyl-1,3,2,4-diathiadiphosphetane 2,4-disulfide; salts of phenyldithio- fluorophosphinic acids; mono- and di-halogenated alkanes
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules200712175

A series of novel ferrocenyl- and aryl-phosphonofluorodithioic salts, adducts, and esters has been prepared. The reaction of 2,4-diferrocenyl-1,3,2,4-diathiadiphosphetane 2,4-disulfide {[FcP(μ-S)S]2, FcLR} with dry KF or tetrabutylammonium fluoride (TBAF) led to the corresponding potassium and tetrabutylammonium salts of ferrocenyldithiofluorophosphinic acids. Treating potassium ferrocenyldithiofluorophosphinic acid with an equimolar amount of tetraphenylphosphonium chloride readily yielded the corresponding organic adducts, and with mono- and di-halogenated alkanes generated a series of the corresponding esters of ferrocenylphosphonofluoridodithioates. Similarly, using 1,3-epithionaphtho[1,8-cd][1,2,6] oxadiphosphinine 1,3-disulfide or Belleau's Reagent in place of FcLR resulted in the corresponding novel salts, adducts, and ester derivatives. All new compounds have been characterized by means of multi-NMR (1H, 13C, 31P, 19F) spectroscopy and accurate mass measurement in conjunction with single crystal X-ray crystallography of four structures.