The bis(methylene) metaphosphite, [P(CH2)2]–, and tris(methylene) metaphosphate, [P(CH2)3]–, families of anions. An experimental and ab initio study

Abstract

Collisional activation of a number of phosphorus-containing anions yields families of negative ions based on bis(methylene) metaphosphite, [P(CH₂)₂]^–, and tris(methylene) metaphosphate, [P(CH₂)₃]^–, structures. Individual product ions produced include [P(CH₂)₂]^–, [CH₂PO]^–, [CH₂PS]^–, [PO₂]^–, [POS]^–, and [PS₂]^–, together with [P(CH₂)₃]^–, [(CH₂)₂PO]^–, [CH₂PO₂]^–, [(CH₂)₂PS]^–, [CH₂P(O)(S)]^–, and [CH₂PS₂]^–. Ab initio calculations indicate that all bonds to phosphorus (in these ions) show appreciable double bond character, and that all methylene-containing phosphorus anions have coplanar atoms except [P(CH₂)₃]^–, which shows out-of-plane twisting of the methylene groups to give an ion of D₃ symmetry.