Theoretical investigations of uranyl-ligand bonding: four- and five-coordinate uranyl cyanide, isocyanide, carbonyl, and hydroxide complexes.
Theoretical investigations of uranyl-ligand bonding: four- and five-coordinate uranyl cyanide, isocyanide, carbonyl, and hydroxide complexes.
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DOI：
10.1021/ic048567u
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发表时间：
2005-03
影响因子：
4.6
通讯作者：
J. L. Sonnenberg;P. Hay;R. L. Martin;B. Bursten
中科院分区：
文献类型：
--
作者：
J. L. Sonnenberg;P. Hay;R. L. Martin;B. Bursten
用密度泛函理论和相对论有效实势研究了赤道氢氧化物、羰基、氰化物（CN-）和异氰化物（NC-）配体与铀酰阳离子[UO 2]2+的配位和成键. [UO_2（OH）_4]~（2-）的几何构型与实验值吻合较好。报道了[UO_2（OH）_5]_3 ~-，[UO_2（CO）_4]_2 ~+，[UO_2（CO）_5]_2 ~+，[UO_2（CN）_4]_2 ~-，[UO_2（CN）_5]_3 ~-，[UO_2（NC）_4]_2 ~-和[UO_2（NC）_5]_3 ~-的新的基态结构预测。四配位的铀酰异氰化物配合物是预测的气相物种，而五配位的铀酰氰化物配合物在水溶液中是积极有利的。氰化物和异氰化物络合物之间的小能量差异表明混合氰化物和异氰化物络合物的能量可行性。一个D2 d四氢氧化铀酰是占主导地位的气相和水的物种，但形成的铀酰羰基络合物被认为是在气相中放热和在水溶液中吸热。
The coordination and bonding of equatorial hydroxide, carbonyl, cyanide (CN-), and isocyanide (NC-) ligands with uranyl dication, [UO2]2+, has been studied using density functional theory with relativistic effective core potentials. Good agreement is seen between experimental and calculated geometries of [UO2(OH)4]2-. Newly predicted ground-state structures of [UO2(OH)5]3-, [UO2(CO)4]2+, [UO2(CO)5]2+, [UO2(CN)4]2-, [UO2(CN)5]3-, [UO2(NC)4]2-, and [UO2(NC)5]3- are reported. Four-coordinate uranyl isocyanide complexes are the predicted gas-phase species while five-coordinate uranyl cyanide complexes are energetically favorable in aqueous solution. Small energy differences between cyanide and isocyanide complexes indicate the energetic feasibility of mixed cyanide and isocyanide complexes. A D2d uranyl tetrahydroxide is the dominant gas-phase and aqueous species, but formation of uranyl carbonyl complexes is seen to be exothermic in the gas-phase and endothermic in aqueous solution.