使用 B(C6F5)3 激活的 Et3SiH 对铀酰离子进行硅烷化。

Silylation of the uranyl ion using B(C6F5)3-activated Et3SiH.

机构信息

Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, California 93106, United States.

出版信息

Inorg Chem. 2011 Oct 3;50(19):9642-9. doi: 10.1021/ic201385h. Epub 2011 Aug 15.

DOI:10.1021/ic201385h

PMID:21842897

Abstract

Addition of 2 equiv of HSiEt(3) to UO(2)((Ar)acnac)(2) ((Ar)acnac = ArNC(Ph)CHC(Ph)O, Ar = 3,5-(t)Bu(2)C(6)H(3)) in the presence of 1 equiv of B(C(6)F(5))(3) results in formation of the U(V) bis(silyloxide) complex [U(OSiEt(3))(2)((Ar)acnac)(2)][HB(C(6)F(5))(3)] (1) in 80% yield. Also produced in the reaction, as a minor product, is U(OSiEt(3))(OB{C(6)F(5)}(3))((Ar)acnac)(2) (2). Interestingly, thermolysis of 1 at 85 °C for 24 h also results in formation of 2, concomitant with production of Et(3)SiH. Addition of 1 equiv of Cp(2)Co to 1 results in formation of U(OSiEt(3))(2)((Ar)acnac)(2) (3) and [Cp(2)Co][HB(C(6)F(5))(3)] (4), which can be isolated in 61% and 71% yields, respectively. Complexes 1-3 have been characterized by X-ray crystallography, while the solution-phase redox properties of 1 have been measured with cyclic voltammetry.

摘要

向 UO(2)((Ar)acnac)(2)（((Ar)acnac = ArNC(Ph)CHC(Ph)O，Ar = 3,5-(t)Bu(2)C(6)H(3)））中加入 2 当量的 HSiEt(3)，并存在 1 当量的 B(C(6)F(5))(3)，得到 U(V) 双(硅氧烷)配合物 [U(OSiEt(3))(2)((Ar)acnac)(2)][HB(C(6)F(5))(3)]（1），产率为 80%。反应中还生成了少量副产物 U(OSiEt(3))(OB{C(6)F(5)}(3))((Ar)acnac)(2)（2）。有趣的是，1 在 85°C 下热解 24 小时也会形成 2，同时生成 Et(3)SiH。向 1 中加入 1 当量的 Cp(2)Co，生成 U(OSiEt(3))(2)((Ar)acnac)(2)（3）和[Cp(2)Co][HB(C(6)F(5))(3)]（4），分别以 61%和 71%的产率分离得到。配合物 1-3 已通过 X 射线晶体学进行了表征，而 1 的溶液相氧化还原性质则通过循环伏安法进行了测量。