Dipnictogen f-Element Chemistry: A Diphosphorus Uranium Complex
- 1 April 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 143 (14), 5343-5348
- https://doi.org/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.Funding Information
- Engineering and Physical Sciences Research Council (EP/K024000/1, EP/M027015/1, EP/P001386/1, EP/S033181/1, EP/T011289/1)
- Royal Society (UF110005)
- Deutsche Forschungsgemeinschaft (SL104/10-1)
- Ministerium f?r Wissenschaft, Forschung und Kunst Baden-W?rttemberg
- Alexander von Humboldt-Stiftung
- FP7 Ideas: European Research Council (612724)
This publication has 54 references indexed in Scilit:
- The Rise of Phosphaethynolate Chemistry in Early Transition Metals, Actinides, and Rare‐Earth ComplexesChemistry – A European Journal, 2019
- The Chemistry of the 2‐Phosphaethynolate AnionAngewandte Chemie, 2018
- P4Activation by Main Group Elements and CompoundsChemical Reviews, 2010
- Early-Transition-Metal-Mediated Activation and Transformation of White PhosphorusChemical Reviews, 2010
- P4 Activation by Late-Transition Metal ComplexesChemical Reviews, 2010
- P2 Addition to Terminal Phosphide M≡P Triple Bonds: A Rational Synthesis of cyclo-P3 ComplexesJournal of the American Chemical Society, 2008
- Triple-Bond Reactivity of Diphosphorus MoleculesScience, 2006
- Diorganophosphanylphosphinidenes as Complexed Ligands: Synthesis via an Anionic Terminal Phosphide of NiobiumAngewandte Chemie, 2004
- The Niobaziridine−Hydride Functional Group: Synthesis and Divergent ReactivityJournal of the American Chemical Society, 2003
- Substituent-Free P1, P2, and P3 Complexes of ZirconiumJournal of the American Chemical Society, 1994