88765-95-1Relevant articles and documents
The Reactivity of Diphosphenes towards Electrophilic and Nucleophilic Reagents
Cowley, Alan H.,Kilduff, Jan E.,Norman, Nicholas C.,Pakulski, Marek
, p. 1801 - 1808 (2007/10/02)
The reaction of P22 (2) with a stoicheiometric quantity of HCl leads to (Me3Si)3CP(H)-P(Cl)C(SiMe3)3 whilst an excess of this reagent causes P=P cleavage and results in the formation of PH(Cl).The corresponding reaction with RP=PR (R = 2,4,6-But3C6H2), (1), results in PH(Cl)R, even when 1 equivalent of HCl is used.Protonation of compound (2) with HBF4.Et2O at -78 deg C results in the phosphonium salt >.Protonation of (1) with HBF4.Et2O is more complex and leads ultimately to P=P bond cleavage and insertion of a cationic phosphorus centre into a C-H bond of an ortho-But group.The dication 2+ and the monocation + and + are formed on treatment of (1) with Ag or .The reaction of (1) with excess of sulphur in the presence of 1,5-diazabicycloundec-5-ene results in P=P bond cleavage and formation of a cyclic dithiophosphinic acid.The diphosphene, (1), reacts with LiMe to afford the anion -.Quenching with MeOH affords the diphosphine R(H)P-P(Me)R, whilst treatment of - with OH- causes P-P bond cleavage and formation of the phosphine oxides PH2RO and PH(Me)RO.Treatment of - with HBF4.Et2O produces PH2R and the phosphonium salt .Treatment of (1) with LiBut also results in anion formation, viz. t)R>-, as the major product which on protonation with MeOH gives the diphosphine R(H)P-P(But)R.The corresponding reaction with LiBun gives the related anion and diphosphine.The reaction of (1) with Ks3> results only in the diphosphine R(H)P-P(H)R>.
