Jian Jiwen, Hu Shu-Xian, Li Wan-Lu, van Stipdonk Michael J, Martens Jonathan, Berden Giel, Oomens Jos, Li Jun, Gibson John K
Chemical Sciences Division , Lawrence Berkeley National Laboratory , Berkeley , California 94720 , United States.
Beijing Computational Science Research Center , Beijing 100193 , People's Republic of China.
Inorg Chem. 2018 Apr 2;57(7):4125-4134. doi: 10.1021/acs.inorgchem.8b00306. Epub 2018 Mar 20.
The following gas-phase uranyl/12-crown-4 (12C4) complexes were synthesized by electrospray ionization: [UO(12C4)] and [UO(12C4)(OH)]. Collision-induced dissociation (CID) of the dication resulted in [UO(12C4-H)] (12C4-H is a 12C4 that has lost one H), which spontaneously adds water to yield [UO(12C4-H)(HO)]. The latter has the same composition as complex [UO(12C4)(OH)] produced by CID of [UO(12C4)(OH)] but exhibits different reactivity with water. The postulated structures as isomeric [UO(12C4-H)(HO)] and [UO(12C4)(OH)] were confirmed by comparison of infrared multiphoton dissociation (IRMPD) spectra with computed spectra. The structure of [UO(12C4-H)] corresponds to cleavage of a C-O bond in the 12C4 ring, with formation of a discrete U-O bond and equatorial coordination by three intact ether moieties. Comparison of IRMPD and computed IR spectra furthermore enabled assignment of the structures of the other complexes. Theoretical studies of the chemical bonding features of the complexes provide an understanding of their stabilities and reactivities. The results reveal bonding and structures of the uranyl/12C4 complexes and demonstrate the synthesis and identification of two different isomers of gas-phase uranyl coordination complexes.
通过电喷雾电离合成了以下气相铀酰/12-冠-4（12C4）配合物：[UO(12C4)]和[UO(12C4)(OH)]。二价阳离子的碰撞诱导解离（CID）产生了[UO(12C4-H)]（12C4-H是失去一个H的12C4），其自发地加水生成[UO(12C4-H)(HO)]。后者与[UO(12C4)(OH)]经CID产生的配合物[UO(12C4)(OH)]具有相同的组成，但与水表现出不同的反应性。通过将红外多光子解离（IRMPD）光谱与计算光谱进行比较，证实了假定的异构[UO(12C4-H)(HO)]和[UO(12C4)(OH)]结构。[UO(12C4-H)]的结构对应于12C4环中一个C-O键的断裂，形成一个离散的U-O键，并由三个完整的醚部分进行赤道配位。此外，IRMPD和计算红外光谱的比较还能确定其他配合物的结构。对配合物化学键特征的理论研究有助于理解它们的稳定性和反应性。结果揭示了铀酰/12C4配合物的键合和结构，并展示了气相铀酰配位配合物两种不同异构体的合成和鉴定。
