Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.
J Am Chem Soc. 2012 Sep 19;134(37):15468-75. doi: 10.1021/ja305712m. Epub 2012 Sep 6.
Addition of 1 equiv of E (E = 0.125 S(8), Se, Te) to U(H(2)C═PPh(3))(NR(2))(3) (R = SiMe(3)) (1) in Et(2)O results in generation of the terminal chalcogenide complexes, [Ph(3)PCH(3)][U(E)(NR(2))(3)] (E = S, 2; Se, 3; Te, 4; R = SiMe(3)), in modest yield. Complexes 2-4 represent extremely rare examples of terminal uranium monochalcogenides. Synthesis of the oxo analogue, [Cp*(2)Co][U(O)(NR(2))(3)] (5), was achieved by reduction of [U(O)(NR(2))(3)] with Cp*(2)Co. All complexes were fully characterized, including analysis by X-ray crystallography. In the solid state, complexes 2-5 feature short U-E bond lengths, suggestive of actinide-ligand multiple bonding.
向（U(H(2)C═PPh(3))(NR(2))(3)）（R = SiMe(3)）（1）在 Et(2)O 中的溶液中加入 1 当量的 E（E = 0.125 S(8), Se, Te），得到末端卤化物配合物[Ph(3)PCH(3)][U(E)(NR(2))(3)]（E = S，2；Se，3；Te，4；R = SiMe(3)），产率适中。配合物 2-4 代表了终端铀单核卤化物的极其罕见的例子。通过 Cp*(2)Co 将[U(O)(NR(2))(3)]还原，合成了偕氧类似物[Cp*(2)Co][U(O)(NR(2))(3)]（5）。所有配合物均通过 X 射线晶体学进行了全面表征。在固态下，配合物 2-5 具有较短的 U-E 键长，表明存在镧系元素-配体多重键。
