硅烷化作用下将铀酰(VI)β-酮亚胺配合物还原为 U(IV)。

Facile reduction of a uranyl(VI) β-ketoiminate complex to U(IV) upon oxo silylation.

机构信息

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

出版信息

Inorg Chem. 2011 Jun 6;50(11):5105-12. doi: 10.1021/ic200387n. Epub 2011 May 5.

DOI:10.1021/ic200387n

Abstract

Reaction of the uranyl β-ketoiminate complex UO(2)((tBu)acnac)(2) (1) ((tBu)acnac = (t)BuNC(Ph)CHC(Ph)O) with Me(3)SiI, in the presence of Ph(3)P, results in the reductive silylation of the uranyl moiety and formation of the U(V) bis-silyloxide complex [Ph(3)PI][U(OSiMe(3))(2)I(4)] (2). Subsequent reaction of 2 with Lewis bases, such as 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), and tetrahydrofuran (THF), results in a further reduction of the metal center and isolation of the U(IV) complexes U(OSiMe(3))(2)I(2)(bipy)(2) (3), U(OSiMe(3))(2)I(2)(phen)(2) (4), and [U(OSiMe(3))(2)I(THF)(4)][I(3)] (5), respectively.

摘要

铀酰β-酮亚胺配合物 UO(2)((tBu)acnac)(2)（1）（(tBu)acnac = (t)BuNC(Ph)CHC(Ph)O）与 Me(3)SiI 的反应，在 Ph(3)P 的存在下，导致铀酰部分的还原硅化，并形成 U(V)双硅氧配合物 [Ph(3)PI][U(OSiMe(3))(2)I(4)]（2）。随后，2 与路易斯碱（如 2,2'-联吡啶（bipy）、1,10-菲咯啉（phen）和四氢呋喃（THF））的反应导致金属中心进一步还原，并分离出 U(IV)配合物 U(OSiMe(3))(2)I(2)(bipy)(2)（3）、U(OSiMe(3))(2)I(2)(phen)(2)（4）和[U(OSiMe(3))(2)I(THF)(4)][I(3)]（5）。