33 / 2023-08-08 03:48:06

Snapshots of Sequential Polyphosphide Rearrangement upon Metallatetrylene Addition

Polyphosphide,Sandwich complexes,Silylene,Main group chemistry,Cooperativity

New Technologies in Phosphorus Chemistry > 4) Inorganic phosphorus chemistry

We present a full study of sequential transformation of the sandwich compounds, pentaphospha- and pentaarsa-ferrocene [Cp*Fe(η⁵-E₅)] (E = P, As)^[1] by a Ga-functionalized silylene.^[2] During the course of the transformation pathway, consecutive migration of the silylene moiety along the polyphosphide or polyarsenide occurred, and a series of different isomers could be identified and isolated.^[3] The isomers resulted from nucleophilic attack (1), ring expansion (2, 4) and ring construction (3, 5). Conversely, when the respective Ga-functionalized germylene was employed, no intermediate was observed and only the stable iron-germylene complex (6) formed. All the isolated compounds represent rare examples of mixed group 13/14 iron polypnictogenides, which could only be achieved by taking advantage of the cooperative effect of the gallatetrylenes with Ga(III)/Si(II) or Ga(III)/Ge(II) entities.