17786-49-1Relevant articles and documents
A Mild One-Pot Reduction of Phosphine(V) Oxides Affording Phosphines(III) and Their Metal Catalysts
Kapu?niak, ?ukasz,Plessow, Philipp N.,Trzybiński, Damian,Wo?niak, Krzysztof,Hofmann, Peter,Jolly, Phillip Iain
supporting information, p. 693 - 701 (2021/04/06)
The metal-free reduction of a range of phosphine(V) oxides employing oxalyl chloride as an activating agent and hexachlorodisilane as reducing reagent has been achieved under mild reaction conditions. The method was successfully applied to the reduction of industrial waste byproduct triphenylphosphine(V) oxide, closing the phosphorus cycle to cleanly regenerate triphenylphosphine(III). Mechanistic studies and quantum chemical calculations support the attack of the dissociated chloride anion of intermediated phosphonium salt at the silicon of the disilane as the rate-limiting step for deprotection. The exquisite purity of the resultant phosphine(III) ligands after the simple removal of volatiles under reduced pressure circumvents laborious purification prior to metalation and has permitted the facile formation of important transition metal catalysts.
REACTION OF PHOSPHOLES WITH ACIDS; PROTON SHIFTS IN 1H-λ5-PHOSPHOLES
Quin, Louis D.,Belmont, Stephen E.,Mathey, Francois,Charrier, Claude
, p. 629 - 634 (2007/10/02)
Addition to phospholes of gaseous HCl at -90 deg C or of an excess of trifluoromethanesulphonic acid at -70 deg C, results in P-protonation.The triflate solutions are stable up to room temperature, but the 1H-phospholium chlorides form PV adducts at -70 deg C, which rapidly rearrange by a sigmatropic H-shift.The observed product is a 1-chloro-2,5-dihydrophospholium chloride.Addition of a chloride ion source to the triflates produces the same result.Unprotonated 3,4-dimethyl-1-phenyl phosphole was found to react at a double bond of its 1H-phospholium ion, forming a crystalline 1,3'-biphospholium dimer.
