Isolable f-element diphosphene complexes by phosphinidene group transfer and coupling at uranium

The parent diphosphene (HPPH) molecule is of fundamental interest, but its reactive nature renders it challenging to isolate and study. Metal-stabilization is an attractive approach for studying HPPH, but molecular derivatives are limited to three complexes of p-/d-metals reflecting a scarcity of synthetic methods for rationally preparing HPPH complexes. Here, we introduce f-element HPPH complexes, adding to f-element diazenes (HNNH) that were first reported over thirty years ago. By utilizing 7λ3-phosphadibenzonorbornadiene and uranium(III) reagents we show how parent diphosphene, phosphinidiide, and diphosphorus motifs can all be constructed, developing synthetic approaches for this area. Computed reaction profiles reveal common, initial reaction steps that subsequently diverge depending on the ancillary ligands, radical nature of intermediates, and the 7λ3-phosphadibenzonorbornadiene P-substituent. Calculations demonstrate a surprising prevalence of open-shell radical intermediates, and that the redox chemistry is P-, not U-, centred. This work thus provides insights to inform future synthetic endeavours in this area.