Applications of boroxide ligands in supporting small molecule activation by U(iii) and U(iv) complexes.
Applications of boroxide ligands in supporting small molecule activation by U(iii) and U(iv) complexes.
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DOI：
10.1039/c8dt05051a
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发表时间：
2019-04
影响因子：
4
通讯作者：
P. Arnold;Laura Puig-Urrea;J. Wells;D. Yuan;Faye L. Cruickshank;Rowan D. Young
中科院分区：
文献类型：
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作者：
P. Arnold;Laura Puig-Urrea;J. Wells;D. Yuan;Faye L. Cruickshank;Rowan D. Young
硼氧化物配体 [OBAr2]- (Ar = Mes, Trip) 首次被证明能够同时支持 UIII 和 UIV 中心。报道了均配和杂配 UIII 和 UIV 复合物的合成和结构。具有较大取代基的 UX3 络合物 [U(OBTrip2)3]2 与较少阻碍的 [U(OBMes2)3]2 相比表现出更高的热稳定性，但与迄今为止测试的较小范围的小分子发生反应。对它们参与小分子化学能力的初步研究表明，深紫色 [U(OBMes2)3]2 结合和/或还原激活多种小分子，例如氧化吡啶、氧化三苯基膦、硫和二环己基碳二亚胺。虽然 [U(OBMes2)3]2 不与 CO 或 CO2 反应，但 [U(OBTrip2)3]2 被两者氧化，在前一种情况下形成 [U(OBTrip2)4]，在后一种情况下形成少量结构特征的 μ-碳酸盐产物 [(μ-CO3){U(OBTrip2)3}2]。
The boroxide ligand [OBAr2]- (Ar = Mes, Trip) is shown to be able to support both UIII and UIV centres for the first time. The synthesis and structures of homoleptic and heteroleptic UIII and UIV complexes are reported. The UX3 complex with larger substituents, [U(OBTrip2)3]2, exhibits greater thermal stability compared to less encumbered [U(OBMes2)3]2 but reacts with a smaller range of the small molecules tested to date. Initial studies on their capacity to participate in small molecule chemistry show that dark purple [U(OBMes2)3]2 binds and/or reductively activates a variety of small molecules such as pyridine-oxide, triphenylphosphineoxide, sulfur, and dicyclohexylcarbodiimide. While [U(OBMes2)3]2 shows no reaction with CO or CO2, [U(OBTrip2)3]2 is oxidised by both, in the former case forming [U(OBTrip2)4], and in the latter case forming a small quantity of the structurally characterised μ-carbonate product [(μ-CO3){U(OBTrip2)3}2].