Isolable f-Element Diphosphene Complexes by Phosphinidene Group Transfer and Coupling at Uranium

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 7<i>l</i>³-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 7<i>l</i>³-phosphadibenzonorbornadiene P-substituent.