Dipnictogen f-Element Chemistry: A Diphosphorus Uranium Complex

The first isolation and structural characterization of an f-element dinitrogen complex was reported in 1988, but an f-element complex with the first heavier group 15 homologue diphosphorus has to date remained unknown. Here, we report the synthesis of a side-on bound diphosphorus complex of uranium(IV) using a 7λ3-(dimethylamino)phosphadibenzonorbornadiene-mediated P atom transfer approach. Experimental and computational characterization reveals that the diphosphorus ligand is activated to its dianionic (P2)2– form and that in-plane U–P π-bonding dominates the bonding of the U(μ-η2:η2-P2)U unit, which is supplemented by a weak U–P interaction of δ symmetry. A preliminary reactivity study demonstrates conversion of this diphosphorus complex to unprecedented uranium cyclo-P3 complexes, suggesting in situ generation of transient, reactive phosphido species.