Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015, Lausanne, Switzerland.
Angew Chem Int Ed Engl. 2016 Mar 14;55(12):4074-8. doi: 10.1002/anie.201600158. Epub 2016 Feb 23.
Thermolysis of the nitride-bridged diuranium(IV) complex Cs{(μ-N)[U(OSi(O(t) Bu)3)3]2} (1) showed that the bridging nitride behaves as a strong nucleophile, promoting N-C bond formation by siloxide ligand fragmentation to yield an imido-bridged siloxide/silanediolate diuranium(IV) complex, Cs{(μ-N(t) Bu)(μ-O2 Si(O(t) Bu)2)U2 (OSi(O(t) Bu)3)5}. Complex 1 displayed reactivity towards CS2 and CO2 at room temperature that is unprecedented in f-element chemistry, affording diverse N-functionalized products depending on the reaction stoichiometry. The reaction of 1 with two equivalents of CS2 yielded the thiocyanate/thiocarbonate complex Cs{(μ-NCS)(μ-CS3 )[U(OSi(O(t)Bu)3)3]2} via a putative NCS(-)/S(2-) intermediate. The reaction of 1 with one equivalent of CO2 resulted in deoxygenation and N-C bond formation, yielding the cyanate/oxo complex Cs{(μ-NCO)(μ-O)[U(OSi(O(t) Bu)3 )3]2}. Addition of excess CO2 to 1 led to the unprecedented dicarbamate product Cs{(μ-NC2O4)[U(OSi(O(t) Bu)3)3]2}.
氮化桥联二铀(IV)配合物 Cs{(μ-N)[U(OSi(O(t)Bu)3)3]2} (1) 的热解表明，桥联氮化物表现出强亲核性，通过硅氧烷配体的断裂促进 N-C 键形成，生成亚氨基桥联硅氧烷/硅烷二醇二铀(IV)配合物 Cs{(μ-N(t)Bu)(μ-O2 Si(O(t)Bu)2)U2 (OSi(O(t)Bu)3)5}。配合物 1 在室温下对 CS2 和 CO2 表现出前所未有的反应活性，根据反应计量比，可得到不同的 N-官能化产物。1 与两当量的 CS2 反应，通过假定的 NCS(-)/S(2-)中间体，生成硫氰酸盐/硫代碳酸盐配合物 Cs{(μ-NCS)(μ-CS3 )[U(OSi(O(t)Bu)3)3]2}。1 与一当量的 CO2 反应导致脱氧和 N-C 键形成，生成氰酸盐/氧代配合物 Cs{(μ-NCO)(μ-O)[U(OSi(O(t)Bu)3)3]2}。向 1 中加入过量的 CO2 导致了前所未有的二氨基甲酸酯产物 Cs{(μ-NC2O4)[U(OSi(O(t)Bu)3)3]2}。
