42847-83-6Relevant academic research and scientific papers
The Reaction of Diethylthiophosphinyl Iodide, Et2P(S)I, with Nucleophiles
Tsivgoulis, Gerasimos M.,Kordopati, Golfo G.,Vachliotis, Dimitris G.,Ioannou, Panayiotis V.
, p. 1075 - 1081 (2017/09/06)
The compound Me2AsSI can exist in two different forms, either as dimethylarsinosulfenyl iodide [or (iodothio)dimethylarsane)], Me2As–S–I (A), or as dimethylthioarsinyl iodide (or dimethylarsinothioic iodide), Me2As(S)–I (B). To confirm that the structure of the product of the reaction between Bunsen's cacodyl disulfide Me2As(S)–S–AsMe2 and iodine is A and not B, the known diethylthiophosphinyl iodide (or diethylphosphinothioic iodide), Et2P(S)–I (2) was prepared and its hydrolytic stability and reactivity towards a variety of nitrogen, phosphorus(III), arsenic(III), oxygen, and sulfur(II) nucleophiles were studied. The results indicated that only a few reactions of 2 resembled those of A, thus strengthening the proposal that the reaction of Bunsen's cacodyl disulfide with iodine produced A and not B. A series of 31P NMR chemical shifts of diethylthiophosphinyl moiety is also reported. Et2P(S)–DMAP, synthesized and isolated during the presented study, is the ethyl analogue of Me2P(S)–DMAP, previously described as an important molecule. In our case, Et2P(S)–DMAP was found to be a good intermediate for the synthesis of phosphoryl or thiophosphoryl derivatives since it was more reactive than 2 towards nucleophiles.
Kinetics and mechanism of the anilinolysis of diethyl thiophosphinic chloride in acetonitrile
Hoque, Md. Ehtesham Ul,Lee, Hai Whang
experimental part, p. 2306 - 2310 (2012/06/01)
The nucleophilic substitution reactions of diethyl thiophosphinic chloride with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated kinetically in acetonitrile at 55.0 °C. The values of deuterium kinetic isotope effects (DKIEs; k H/kD) invariably increase from secondary inverse (k H/kD H/k D > 1) as the nucleophiles change from the strongly basic to weakly basic anilines. The secondary inverse with the strongly basic anilines and primary normal DKIEs with the weakly basic anilines are rationalized by the gradual transition state (TS) variation from a predominant backside attack, via invariably increasing the fraction of a frontside attack, to a predominant frontside attack, in which the reaction mechanism is a concerted SN2 pathway. A frontside attack involving a hydrogen bonded, four-center-type TS is substantiated by the primary normal DKIEs.
Phosphinothioic Organylamidato Complexes 2Ni, Planar-Tetrahedral Chelates with Metal-Nitrogen-Sulfur Chromophores
Fuchs, Manfred,Kuchen, Wilhelm,Peters,Wilfried
, p. 1569 - 1580 (2007/10/02)
Reaction of -Li+ with NiHal2 in inert solvents gave extremely hydrolyzable complexes 2Ni (R = Me, iPr, tBu, cHex, Ph) 3a-f containing four-membered chelate rings and NiN2S2 chromophores.It is shown by magnetic measurements, electronic and 31P NMR spectroscopy that 3d (R=tBu) is purely tetrahedral over a wide range of temperature as well in the solid state as in solution.In solutions of the other compounds 3, there exists an equilibrium planar tetrahedral, the latter isomer prevailing with larger R and with increasing temperature. 3a and 3b (R = Me, Et) are almost entirely planar at room temperature.In solid state 3a is most probably pentacoordinated and 3c a mixture of both isomers, while 3e is tetrahedral and 3f planar.
