A Complete Family of Terminal Uranium Chalcogenides, [U(E)(N{SiMe3}2)3]- (E = O, S, Se, Te)
A Complete Family of Terminal Uranium Chalcogenides, [U(E)(N{SiMe3}2)3]- (E = O, S, Se, Te)
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DOI：
10.1021/ja305712m
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发表时间：
2012-09-19
影响因子：
15
通讯作者：
Hayton, Trevor W.
中科院分区：
文献类型：
--
作者：
Brown, Jessie L.;Fortier, Skye;Hayton, Trevor W.
在Et 2 O中将1当量的E（E = 0.125 S-g，Se，Te）加入到U（H2 C = PPh 3）（NR 2）（3）（R = SiMe 3）（1）中，导致以适度产率产生末端硫属化物络合物[Ph 3 PCH 3][U（E）（NR 2）（3）]（E = S，2; Se，3; Te，4; R = SiMe 3）。配合物2-4代表了极其罕见的终端铀单硫族化物的例子。通过用Cp*2CO还原[U（O）（NR 2）（3）]来实现氧代类似物[Cp*Co-2][U（O）（NR 2）（3）]（5）的合成。所有的配合物进行了充分的表征，包括通过X射线晶体学分析。在固态下，配合物2-5的特征是短的U-E键长，暗示锕系元素-配体多重键合。
Addition of 1 equiv of E (E = 0.125 S-g, Se, Te) to U(H2C=PPh3)(NR2)(3) (R = SiMe3) (1) in Et2O results in generation of the terminal chalcogenide complexes, [Ph3PCH3][U(E)(NR2)(3)] (E = S, 2; Se, 3; Te, 4; R = SiMe3), in modest yield. Complexes 2-4 represent extremely rare examples of terminal uranium monochalcogenides. Synthesis of the oxo analogue, [Cp*Co-2][U(O)(NR2)(3)] (5), was achieved by reduction of [U(O)(NR2)(3)] with Cp*2CO. 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.