Dipnictogen f-Element Chemistry: A Diphosphorus Uranium Complex
Dipnictogen f-Element Chemistry: A Diphosphorus Uranium Complex
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DOI：
10.1021/jacs.1c02482
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发表时间：
2021-04-01
影响因子：
15
通讯作者：
Liddle, Stephen T.
中科院分区：
文献类型：
--
作者：
Du, Jingzhen;Hunger, David;Liddle, Stephen T.
1988年首次报道了f-元素双氮复合物的分离和结构表征，但迄今为止，f-元素与第一个较重的15族同源物二磷的复合物仍然未知。在这里，我们报告了使用7 λ（3）-（二甲氨基）phosphodibenzonorbornadienemediated的P原子转移方法合成的侧上结合的双磷配合物的铀（IV）。实验和计算表征表明，二磷配体被活化为其双阴离子（P-2）（2-）形式，并且平面内U-P π键合主导U（mu-eta（2）：eta（2）-P-2）U单元的键合，其由δ对称的弱U-P相互作用补充。初步的反应性研究表明，这种二磷配合物前所未有的铀cyclo-P-3配合物的转换，表明在原位生成的瞬态，反应性的phosphido物种。
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.