A new synthetic route to aminophosphines

The reactions of R₂PPR₂ (R = Me, Et, Ph) and (MeP)₅ with Me_3−nAs(NMe₂)_n (n = 1, 2, 3) and of Me₂PPMe₂ with Me₂AsNR′₂ (R′ = Et, Prⁿ, and Prⁱ) were investigated as a function of time at room temperature using ¹H and ³¹P NMR spectroscopy. For the diphosphine/Me₂AsNR′₂ reactions, the NMR spectral data suggest a reaction pathway involving the initial formation of R₂PAsMe₂ and the respective acyclic dialkylaminophosphine, R₂PNR′₂. The P---As intermediate then symmetrizes to R₂PPR₂ and Me₂AsAsMe₂, the parent aminoarsine is completely consumed, and additional R₂PNR′ is formed. The relative rate of aminophosphine production is dependent upon the nature of the substituent on the phosphorus and nitrogen atoms. For systems involving MeAs(NMe₂)₂ and As(NMe₂)₃ as reactants, the intermediates could not be characterized, but the products were the expected aminophosphine and (MeAs)₅ or elemental arsenic, respectively. (MeP)₅ reacts to give MeP(NMe₂)₂ and the expected As---As bonded species. A comparison of the reactivity of these systems with analogous diarsine/aminoarsine systems is discussed. The results of the NMR study were utilized in designing a convenient, high yield, synthetic route to acyclic aminophosphines.