Facile Reduction of a Uranyl(VI) β-ketoiminate Complex to U(IV) Upon Oxo Silylation
Facile Reduction of a Uranyl(VI) β-ketoiminate Complex to U(IV) Upon Oxo Silylation
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DOI：
10.1021/ic200387n
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发表时间：
2011-06-06
影响因子：
4.6
通讯作者：
Hayton, Trevor W.
中科院分区：
文献类型：
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作者：
Brown, Jessie L.;Mokhtarzadeh, Charles C.;Hayton, Trevor W.
在Ph(3)P存在下，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反应，导致铀酰部分还原硅基化，生成U(V)双硅氧基配合物[Ph(3)PI][U(OSiMe(3))(2)I(4)](2).2与Lewis碱，如2，2‘-联吡啶(Bipy)、1，10-菲咯啉(Phen)和四氢呋喃(THF)的后续反应，导致金属中心的进一步还原和U(IV)配合物U(OSiMe(3))(2)I(2)(2)(3)，U(OSiMe(3))(2)I(2)-(Phen)(2)和[U(OSiMe(3))(2)I(THF)(4)][I(3)](5)，分别进行了分析。
Reaction of the uranyl beta-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.