Du Jingzhen, Hunger David, Seed John A, Cryer Jonathan D, King David M, Wooles Ashley J, van Slageren Joris, Liddle Stephen T
Department of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, U.K.
Institute of Physical Chemistry, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany.
J Am Chem Soc. 2021 Apr 14;143(14):5343-5348. doi: 10.1021/jacs.1c02482. Epub 2021 Apr 1.
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 7λ-(dimethylamino)phosphadibenzonorbornadiene-mediated P atom transfer approach. Experimental and computational characterization reveals that the diphosphorus ligand is activated to its dianionic (P) form and that in-plane U-P π-bonding dominates the bonding of the U(μ-η:η-P)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 -P complexes, suggesting generation of transient, reactive phosphido species.
1988年报道了首例f元素二氮配合物的分离和结构表征，但迄今为止，含有第一主族较重同系物二磷的f元素配合物仍不为人知。在此，我们报道了一种使用7λ-（二甲氨基）磷杂二苯并降冰片二烯介导的P原子转移方法合成的铀（IV）侧基配位二磷配合物。实验和计算表征表明，二磷配体被激活为其二价阴离子（P）形式，并且面内U-P π键主导了U（μ-η:η-P）U单元的键合，同时还存在弱的δ对称U-P相互作用。初步的反应性研究表明，这种二磷配合物可转化为前所未有的铀-磷配合物，这表明生成了瞬态的、具有反应性的磷化物物种。
