Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.
J Am Chem Soc. 2010 Jun 2;132(21):7248-9. doi: 10.1021/ja1013739.
Addition of Me(3)SiI to UO(2)((Ar)acnac)(2) (ArNC(Ph)CHC(Ph)O, Ar = 3,5-(t)Bu(2)C(6)H(3)) (1) results in the formation of U(OSiMe(3))(2)I(2)((Ar)acnac) (2) in moderate yield. Also formed in the reaction are I(2) and ArNC(Ph)=CHC(Ph)OSiMe(3), the product of (Ar)acnac abstraction by Me(3)Si(+). In contrast, reaction of 1 with Me(3)SiX (X = Cl, OTf) only results in the formation of UO(2)(OTf)(2)((Ar)acnacH)(2)(Et(2)O) (3) and UO(2)Cl(2)((Ar)acnacH)(2) (4), respectively.
向 UO(2)((Ar)acnac)(2)(ArNC(Ph)CHC(Ph)O,Ar = 3,5-(t)Bu(2)C(6)H(3))(1)中加入 Me(3)SiI,可得到中等产率的 U(OSiMe(3))(2)I(2)((Ar)acnac)(2)。反应中还形成了 I(2)和 ArNC(Ph)=CHC(Ph)OSiMe(3),这是 Me(3)Si(+)对(Ar)acnac的抽提产物。相比之下,1 与 Me(3)SiX(X = Cl,OTf)的反应仅分别生成 UO(2)(OTf)(2)((Ar)acnacH)(2)(Et(2)O)(3)和 UO(2)Cl(2)((Ar)acnacH)(2)(4)。