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

doi:10.1021/jacs.1c02482

Dipnictogen f-Element Chemistry: A Diphosphorus Uranium Complex

J Am Chem Soc. 2021 Apr 14;143(14):5343-5348. doi: 10.1021/jacs.1c02482. Epub 2021 Apr 1.

Authors

Jingzhen Du¹, David Hunger², John A Seed¹, Jonathan D Cryer¹, David M King³, Ashley J Wooles¹, Joris van Slageren², Stephen T Liddle¹

Affiliations

¹ Department of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, U.K.
² Institute of Physical Chemistry, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany.
³ School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, U.K.

PMID: 33792307
DOI: 10.1021/jacs.1c02482

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.