Radical anionic versus neutral 2,2′-bipyridyl coordination in uranium complexes supported by amide and ketimide ligands

被引：22
|
作者：
Diaconescu, Paula L. [1 ]
Cummins, Christopher C. [1 ]
机构：
[1] MIT, Dept Chem, Cambridge, MA 02139 USA
来源：
DALTON TRANSACTIONS | 2015年 / 44卷 / 06期
基金：
美国国家科学基金会;
关键词：
BRIDGED DIURANIUM COMPLEXES; LANTHANIDE COMPLEXES; MOLECULAR-STRUCTURES; ELECTRONIC-STRUCTURE; MIT 2,2'-DIPYRIDYL; NITROGEN BASES; CRYSTAL; CHARGE; STATE; REACTIVITY;
D O I：
10.1039/c4dt02422b
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The synthesis and characterization of (bipy)(2)U(N[t-Bu]Ar)(2) (1-(bipy)(2), bipy = 2,2'-bipyridyl, Ar = 3,5-C6H3Me2), (bipy)U(N[(1)Ad]Ar)(3) (2-bipy), (bipy)(2)U(NC[t-Bu]Mes)(3) (3-(bipy)(2), Mes = 2,4,6-C6H2Me3), and IU(bipy)(NC[t-Bu]Mes)(3) (3-I-bipy) are reported. X-ray crystallography studies indicate that bipy coordinates as a radical anion in 1-(bipy) and 2-bipy, and as a neutral ligand in 3-I-bipy. In 3-(bipy)(2), one of the bipy ligands is best viewed as a radical anion, the other as a neutral ligand. The electronic structure assignments are supported by NMR spectroscopy studies of exchange experiments with 4,4'-dimethyl-2,2'-bipyridyl and also by optical spectroscopy. In all complexes, uranium was assigned a + 4 formal oxidation state.
引用
收藏
页码：2676 / 2683
页数：8
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