[2π+2π] Cycloaddition of Isocyanates to Uranium(IV) Imido Complexes for the Synthesis of U(IV) κ2-Ureato Compounds.
[2π+2π] Cycloaddition of Isocyanates to Uranium(IV) Imido Complexes for the Synthesis of U(IV) κ2-Ureato Compounds.
复制标题
[2π+2π] 异氰酸酯与铀 (IV) 亚氨基配合物的环加成反应用于合成 U(IV) κ2-脲基化合物。
DOI：
10.1021/acs.inorgchem.6b02547
复制
发表时间：
2017
影响因子：
4.6
通讯作者：
Suzanne C. Bart
中科院分区：
文献类型：
--
作者：
Caleb J. Tatebe;M. Zeller;Suzanne C. Bart
以Tp*2UBn为原料，通过联苯挤压合成了一族新的铀(IV)亚胺配合物Tp*2U(NR)(Tp*=氢三(3，5-二甲基吡唑基)硼酸酯；R=苄基(Bn)、对甲苯(p-Tol)、2，6-二乙基苯基(DETP)和2，6-二异丙基苯基(DIPP))。TP*2U(NBN)、TP*2U(NP-TOL)和TP*2U(NDETP)，以及先前报道的TP*2U(NPH)和TP*2U(NAD)(Ad=1-金刚烷基)，很容易与异氰酸酯和异硫氰酸酯进行[2π+2π]环加成，分别生成κ2-尿素和κ2-硫脲衍生物。这些新的铀(IV)配合物通过多核核磁共振、振动和电子吸收光谱进行了表征，并在可能的情况下通过X射线结晶学进行了表征。用计算模型定量计算了配体的空间需求，结果表明，只有当配体占据配位球的90%或更少时，才会发生环加成反应。
A new family of uranium(IV) imido complexes of the form Tp*2U(NR) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate; R = benzyl (Bn), para-tolyl (p-Tol), 2,6-diethylphenyl (detp), and 2,6-diisopropylphenyl (dipp)) have been generated by bibenzyl extrusion from Tp*2UBn. Tp*2U(NBn), Tp*2U(Np-Tol), and Tp*2U(Ndetp), along with previously reported Tp*2U(NPh) and Tp*2U(NAd) (Ad = 1-adamantyl), readily undergo [2π+2π] cycloaddition with isocyanates and isothiocyanates to generate κ2-ureato and κ2-thioureato derivatives, respectively. These new uranium(IV) complexes were characterized via multinuclear NMR, vibrational and electronic absorption spectroscopies, and, where possible, X-ray crystallography. The steric demands of the ligands were quantitatively assessed using computational modeling, and it was shown that cycloaddition only occurs for imido species where ligands occupy 90% or less of the coordination sphere.
影响因子：
4.9
作者：
Castro-Rodríguez, I;Meyer, K
通讯作者：
Meyer, K
影响因子：
6.6
作者：
Duncan, AP;Bergman, RG
通讯作者：
Bergman, RG