Dipnictogen f-Element Chemistry: A Diphosphorus Uranium Complex
Jingzhen Du, David Hunger, John A. Seed, Jonathan D. Cryer, David M. King, Ashley J. Wooles, Joris van Slageren, Stephen T. Liddle
Abstract
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.