Systematic Investigation of Thorium(IV)- and Uranium(IV)-Ligand Bonding in Dithiophosphonate, Thioselenophosphinate, and Diselenophosphonate Complexes
Systematic Investigation of Thorium(IV)- and Uranium(IV)-Ligand Bonding in Dithiophosphonate, Thioselenophosphinate, and Diselenophosphonate Complexes
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DOI：
10.1021/ic401642a
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发表时间：
2013-09-16
影响因子：
4.6
通讯作者：
Walensky, Justin R.
中科院分区：
文献类型：
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作者：
Behrle, Andrew C.;Barnes, Charles L.;Walensky, Justin R.
由ThCl_4（DME）（2）或UI_4之间的盐复分解合成了通式An[E_2PROR ′]（4）的均配型软给体锕系元素配合物（1，4-二氧六环）（2）和M[E2 PROR ′]（M = Na，K），得到2（An = Th，E = S，R = 4-MeOC 6H4，R' = Me），3（An = Th，E = S，R = 4-MeOC 6H4，R' = Bu-t），4 5（An = Th，E = Se，R = C6H5，R ′ = Me）和6（An = U，E = Se，R = C6H5，R ′ = Me）。此外，ThCl_4（DME）（2）和Ul（4）（1，4-二氧六环）（2）与Na[SSePPh_2]反应，分别生成了钍和铀的硫代硒代次膦酸配合物7和8。所有化合物的特征在于使用元素分析，H-1和P-31 NMR，和IR光谱，和U（IV）化合物也进行了检查与紫外可见光谱。5的Se-77 NMR谱揭示了首次报道的与Th-Se键的共振。通过X射线晶体学测定了2、5、7和8的固态结构。的锕系元素-配体键合进行了研究，使用密度泛函理论计算结合量子理论的原子在分子中的分析，并显示稍微增加的共价性，在锕系元素-硒键比锕系元素-硫。
Homoleptic soft-donor actinide complexes of the general form An[E2PROR'](4) were synthesized from salt metathesis between ThCl4(DME)(2) or UI4(1,4-dioxane)(2) and M[E2PROR'], M = Na, K, to yield 2 (An = Th, E = S, R = 4-MeOC6H4, R' = Me), 3 (An = Th, E = S, R = 4-MeOC6H4, R' = Bu-t), 4 (An = U, E = S, R = 4-MeOC6H4, R' = Me), 5 (An = Th, E = Se, R = C6H5, R' = Me), and 6 (An = U, E = Se, R = C6H5, R' = Me). In addition thorium and uranium thioselenophosphinate complexes 7 and 8 were produced from the reaction of ThCl4(DME)(2) and Ul(4)(1,4-dioxane)(2) and Na[SSePPh2], respectively. All compounds were characterized using elemental analysis, H-1 and P-31 NMR, and IR spectroscopy, and the U(IV) compounds were also examined with UV-vis spectroscopy. The Se-77 NMR spectrum of 5 reveals the first reported resonance with a Th-Se bond. The solid-state structures of 2, 5, 7, and 8 were determined by X-ray crystallography. The actinide-ligand bonding was examined using density functional theory calculations in conjunction with quantum theory of atoms-in-molecules analysis and shows slightly increased covalency in actinide-selenium bonds than actinide-sulfur.