Dithio- and Diselenophosphinate Thorium(IV) and Uranium(IV) Complexes: Molecular and Electronic Structures, Spectroscopy, and Transmetalation Reactivity.
Dithio- and Diselenophosphinate Thorium(IV) and Uranium(IV) Complexes: Molecular and Electronic Structures, Spectroscopy, and Transmetalation Reactivity.
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DOI：
10.1021/acs.inorgchem.5b01342
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发表时间：
2015-12
影响因子：
4.6
通讯作者：
Andrew C. Behrle;A. Kerridge;J. Walensky
中科院分区：
文献类型：
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作者：
Andrew C. Behrle;A. Kerridge;J. Walensky
本文报道了二硫代和二硒代膦酸盐（E_2PR_2）（1-）（E = S，Se; R =（i）Pr，（t）Bu）与钍（IV）和铀（IV）配合物的分子结构和电子结构的比较。对于二硫代次膦酸钍配合物，ThCl_4（DME）_2与4当量KS_2PR_2（R =（i）Pr，（t）Bu）反应生成均配配合物Th（S_2P（i）Pr_2）_4（1S-Th-（i）Pr）和Th（S_2P（t）Bu_2）_4（2S-Th-（t）Bu）。使用KSe2PR 2以类似的方式合成二硒次膦酸盐络合物以产生Th（Se2P（i）Pr2）4（1Se-Th-（i）Pr）和Th（Se2P（t）Bu2）4（2Se-Th-（t）Bu）。U（S_2P（i）Pr_2）_4，1S-U-（i）Pr，可由UCl_4和4当量的KS_2P（i）Pr_2直接制得。对于（Se2P（i）Pr2）（1-），使用UCl 4和3或4当量的KSe2P（i）Pr2产生单氯化物产物U（Se2P（i）Pr2）3Cl（3Se-U（iPr）-Cl），但使用UI 4（1，4-二氧六环）2产生均配型U（Se2P（i）Pr2）4（1Se-U-（i）Pr）。类似地，UCl 4与4当量的KS2P（t）Bu2的反应产生U（S2P（t）Bu2）4（2S-U-（t）Bu），而与KSe 2P（t）Bu2的反应导致形成U（Se 2P（t）Bu2）3Cl（4Se-U（tBu）-Cl）。使用UI4（1，4-二氧六环）2和4当量KSe2P（t）Bu2与UCl4的乙腈溶液，得到U（Se2P（t）Bu2）4（2Se-U-（t）Bu）。研究了用络合物2Se-U-（t）Bu和各种CuX（X = Br，I）盐的金属转移反应，以产生U（Se2P（t）Bu 2）3X（6Se-U（tBu）-Br和7Se-U（tBu）-I）和0.25当量的[Cu（Se2P（t）Bu 2）] 4（8Se-Cu-（t）Bu）。2Se-U-（t）Bu与Hg_2F_2和ZnCl_2发生金属转移反应，分别得到U（Se_2P（t）Bu_2）_3F（6）和U（Se_2P（t）Bu_2）_3Cl（4Se-U（tBu）-Cl）。使用（1）H、（13）C、（31）P和（77）Se NMR和IR光谱分析分子结构，并使用X射线晶体学进行结构表征。使用QTAIM的方法，所有homoleptic配合物的电子结构进行了探测，在锕系元素-硒键比锕系元素-硫键的共价键特征稍多。
We report a comparison of the molecular and electronic structures of dithio- and diselenophosphinate, (E2PR2)(1-) (E = S, Se; R = (i)Pr, (t)Bu), with thorium(IV) and uranium(IV) complexes. For the thorium dithiophosphinate complexes, reaction of ThCl4(DME)2 with 4 equiv of KS2PR2 (R = (i)Pr, (t)Bu) produced the homoleptic complexes, Th(S2P(i)Pr2)4 (1S-Th-(i)Pr) and Th(S2P(t)Bu2)4 (2S-Th-(t)Bu). The diselenophosphinate complexes were synthesized in a similar manner using KSe2PR2 to produce Th(Se2P(i)Pr2)4 (1Se-Th-(i)Pr) and Th(Se2P(t)Bu2)4 (2Se-Th-(t)Bu). U(S2P(i)Pr2)4, 1S-U-(i)Pr, could be made directly from UCl4 and 4 equiv of KS2P(i)Pr2. With (Se2P(i)Pr2)(1-), using UCl4 and 3 or 4 equiv of KSe2P(i)Pr2 yielded the monochloride product U(Se2P(i)Pr2)3Cl (3Se-U(iPr)-Cl), but using UI4(1,4-dioxane)2 produced the homoleptic U(Se2P(i)Pr2)4 (1Se-U-(i)Pr). Similarly, the reaction of UCl4 with 4 equiv of KS2P(t)Bu2 yielded U(S2P(t)Bu2)4 (2S-U-(t)Bu), whereas the reaction with KSe2P(t)Bu2 resulted in the formation of U(Se2P(t)Bu2)3Cl (4Se-U(tBu)-Cl). Using UI4(1,4-dioxane)2 and 4 equiv of KSe2P(t)Bu2 with UCl4 in acetonitrile yielded U(Se2P(t)Bu2)4 (2Se-U-(t)Bu). Transmetalation reactions were investigated with complex 2Se-U-(t)Bu and various CuX (X = Br, I) salts to yield U(Se2P(t)Bu2)3X (6Se-U(tBu)-Br and 7Se-U(tBu)-I) and 0.25 equiv of [Cu(Se2P(t)Bu2)]4 (8Se-Cu-(t)Bu). Additionally, 2Se-U-(t)Bu underwent transmetalation reactions with Hg2F2 and ZnCl2 to yield U(Se2P(t)Bu2)3F (6) and U(Se2P(t)Bu2)3Cl (4Se-U(tBu)-Cl), respectively. The molecular structures were analyzed using (1)H, (13)C, (31)P, and (77)Se NMR and IR spectroscopy and structurally characterized using X-ray crystallography. Using the QTAIM approach, the electronic structure of all homoleptic complexes was probed, showing slightly more covalent bonding character in actinide-selenium bonds over actinide-sulfur bonds.