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 7 lambda(3)-(dimethylamino)phosphadibenzonorbornadienemediated P atom transfer approach. Experimental and computational characterization reveals that the diphosphorus ligand is activated to its dianionic (P-2)(2-) form and that in-plane U-P pi-bonding dominates the bonding of the U(mu-eta(2):eta(2)-P-2)U unit, which is supplemented by a weak U-P interaction of delta symmetry. A preliminary reactivity study demonstrates conversion of this diphosphorus complex to unprecedented uranium cyclo-P-3 complexes, suggesting in situ generation of transient, reactive phosphido species.

Automated summary

This study reports the synthesis of a uranium diphosphorus complex with a unique structure and reactivity through a P atom transfer approach. Experimental and computational characterization reveal the activation of the diphosphorus ligand and the presence of distinctive U-P bonding interactions.