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 homolog diphosphorus has to date remained unknown. Here, we report the synthesis of a side-on bound diphosphorus complex of uranium(IV) using a 7l3-(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 p-bonding dominates the bonding of the U(μ-h2:h2-P2)U unit and this is supplemented by a weak U-P interaction of d 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.