硼烷促进的金属氧配体硅烷化反应。

Borane-mediated silylation of a metal-oxo ligand.

机构信息

Department of Chemistry and Biochemistry, University of California at Santa Barbara, Santa Barbara, California 93106, USA.

出版信息

Inorg Chem. 2011 Jun 6;50(11):4695-7. doi: 10.1021/ic2008649. Epub 2011 May 9.

DOI:10.1021/ic2008649

PMID:21553868

Abstract

The addition of 1 equiv of HSiPh(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 the formation of U(OSiPh(3))(OB{C(6)F(5)}(3))((Ar)acnac)(2) (1), via silylation of an oxo ligand and reduction of the uranium center. The addition of 1 equiv of Cp(2)Co to 1 results in a reduction to uranium(IV) and the formation of [Cp(2)Co][U(OSiPh(3))(OB{C(6)F(5)}(3))((Ar)acnac)(2)] (2) in 78% yield. Complexes 1 and 2 have been characterized by X-ray crystallography, while the solution-phase redox properties of 1 have been measured with cyclic voltammetry.

摘要

向 UO2((Ar)acnac)2（(Ar)acnac = ArNC(Ph)CHC(Ph)O；Ar = 3,5-(t)Bu2C6H3）中加入 1 当量的 HSiPh(3)，同时存在 1 当量的 B(C6F5)3，通过肟配体的硅烷基化和铀中心的还原，生成了 U(OSiPh(3))(OB{C6F5}(3))((Ar)acnac)(2)（1）。向 1 中加入 1 当量的 Cp2Co，导致铀还原为铀(IV)，并以 78%的产率生成[Cp2Co][U(OSiPh(3))(OB{C6F5}(3))((Ar)acnac)(2)]（2）。复合物 1 和 2 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。