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The Reactivity of Diphosphenes towards Electrophilic and Nucleophilic Reagents

DOI: 10.1039/DT9860001801

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1801 - 1808 (1986)

Update date:2022-08-04

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Authors:

Cowley, Alan H.Cowley, Alan H.

Kilduff, Jan E.Kilduff, Jan E.

Norman, Nicholas C.Norman, Nicholas C.

Pakulski, MarekPakulski, Marek

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Article abstract of DOI:10.1039/DT9860001801

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-diazabicyclo<5.4.0>undec-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>.

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Product name:((((CH3)3C)3C6H2)P)2Ag2(2+)

Cas No:94780-38-8

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