Oxydation Et Isomerisation De Diphosphene

Selective monooxygenation of diphosphenes with molecular oxygen

“…2 Although their reaction chemistry has also been widely investigated, an oxygen-atom adduct of the diphosphene, i.e., diphosphene oxide, formulated as (R)(Ov)PvP(R) (II), has only rarely been explored. 3,4 Recently, dioxygen (O 2 ) splitting mediated by low-valent phosphorus species have been extensively investigated, mainly producing (PO 2 ) n (n = 1 or 2) moieties. 5 Oxidation of the diphosphene I is, however, not very simple.…”

“…The Mes*-based diphosphene, (Mes*)PP(Mes*) ( A ), is air- and moisture-stable in the solid state at room temperature, but gradually decomposed in toluene at 80 °C under the atmosphere of molecular oxygen, triplet dioxygen ( 3 O 2 ), giving monophosphorus compounds, along with a scission of the PP double bond [Scheme 1(a)]. 4 In contrast, A quickly reacted with photochemically generated singlet dioxygen ( 1 O 2 ) at −78 °C to form a mixture of diphosphene oxide ( B ) and dioxodiphosphetane ( C ), then yielding hydrolysis products [Scheme 1(b)]. 4 The diphosphene A also reacted with m -chloroperoxybenzoic acid ( m CPBA) to generate B , which further reacted with m -chlorobenzoic acid, then water to give hydrolysis products [Scheme 1(c)].…”

“…4 In contrast, A quickly reacted with photochemically generated singlet dioxygen ( 1 O 2 ) at −78 °C to form a mixture of diphosphene oxide ( B ) and dioxodiphosphetane ( C ), then yielding hydrolysis products [Scheme 1(b)]. 4 The diphosphene A also reacted with m -chloroperoxybenzoic acid ( m CPBA) to generate B , which further reacted with m -chlorobenzoic acid, then water to give hydrolysis products [Scheme 1(c)]. 3 It is noteworthy that the intermediate B formed in the above reactions is possible to isolate as a stable compound by the reaction of a phosphonic dichloride, (Mes*)(O)PCl 2 ( D ), with magnesium metal [Scheme 1(d)].…”