Notizen: Beiträge zur Chemie des Phosphors, 52.

Unusual Intermolecular “Through-Space” J Couplings in P–Se Heterocycles

“…In this work, solid-state NMR spectroscopy of novel P-Se heterocycles demonstrates the presence not just of intramolecular through-space J couplings, but also of unusual through-space intermolecular couplings that direct the three-dimensional solid-state structure, and use periodic DFT calculations to understand their origin. Two novel selenium phosphorous naphthalenes (1 and 2) were prepared following an adapted route, [17][18] using tertiary phosphines under an oxygen and moisture-free atmosphere, as shown in Scheme 1.…”

Structure–property-reactivity studies on dithiaphospholes

“…Reduction of the chloride salt 1a has previously been achieved using sodium metal to form 4. 23 However we found that the rate of reduction of both 1a and 2a was particularly sensitive to the size of the sodium pieces employed. Initial studies required two to four days to ensure complete reduction (monitored by 31 P NMR spectroscopy) but initial pre-treatment of a suspension of small pieces of sodium metal in toluene (100°C, 20 min) afforded a fine sodium dispersion which led to shorter reaction times (ca.…”

“…Synthesis P-Halo-benzodithiaphospholes were prepared by Baudler 23 in 1973 who showed that reduction led to P-P coupling to form the σ-bonded dimers 4 and 5 (Scheme 2). Burford showed that treatment of these P-halo dithiaphospholes with Lewis acids (AlCl 3 or GaCl 3 ) forms the corresponding dithiaphosphenium salts (Scheme 2).…”

Synthesis of bis(trithio)phosphines by oxidative transfer of phosphorus(i)

“…In the current work we describe our first foray into this area where we examine the oxidative addition of tetrathiocins to the phosphorus(I) transfer agent, [P I dppe][Br], to generate the benzo-dithiophosphinyl framework (Scheme 4, 1) containing formal phosphorus(II) centres in addition to compounds 2 and 3 which feature formal phosphorus (III) environments. It should be noted that work on such benzo-fused C2S2P heterocycles was initially reported by Baudler 32 and subsequent studies by Burford focused on the structure and Lewis acidity of divalent benzodithiaphosphenium cations derived . [33][34][35][36] Related classes of thiophosphines have been shown to have many industrial applications such as antioxidants for lubricants and oils, 37 and are traditionally synthesized from highly reactive and poisonous white phosphorus.…”