Abstract
AbstractThe reaction of several amino‐substituted mono‐ and dichlorophosphanes (R2N)nPCl3–n(n= 2, R =i‐Pr;n= 1, R =i‐Pr, Cy) with GaCl3to form phosphenium cations [(i‐Pr2N)2P]+(13+) and [(R2N)PCl]+(14a, b+) has been investigated. The isolation and fully characterization of the first amino‐ and chloro‐substituted phosphenium cation14b[GaCl4] was accomplished. The insertion of these phosphenium ions into P–P bonds of dissolved P4was examined. Amino‐ and chloro‐substituted phosphenium cations14a, b+readily form the corresponding P5+‐cages15a, b+. No reaction was observed for the less electrophilic diamino‐substituted phosphenium cation13+. The molecular structures of [14b][GaCl4] and [15b][Ga2Cl7] are presented and, furthermore, the intriguing NMR spectra of the P5+‐cations15a, b+are discussed.
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