Dithio- and Diselenophosphinate Thorium(IV) and Uranium(IV) Complexes: Molecular and Electronic Structures, Spectroscopy, and Transmetalation Reactivity

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• 作者：Andrew C. Behrle ; Andrew Kerridge ; Justin R. Walensky
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：December 21, 2015
• 年：2015
• 卷：54
• 期：24
• 页码：11625-11636
• 全文大小：520K
• ISSN：1520-510X

文摘

We report a comparison of the molecular and electronic structures of dithio- and diselenophosphinate, (E₂PR₂)^{1鈥?/sup> (E = S, Se; R = iPr, tBu), with thorium(IV) and uranium(IV) complexes. For the thorium dithiophosphinate complexes, reaction of ThCl₄(DME)₂ with 4 equiv of KS₂PR₂ (R = iPr, tBu) produced the homoleptic complexes, Th(S₂PiPr₂)₄ (1S-Th-iPr) and Th(S₂PtBu₂)₄ (2S-Th-tBu). The diselenophosphinate complexes were synthesized in a similar manner using KSe₂PR₂ to produce Th(Se₂PiPr₂)₄ (1Se-Th-iPr) and Th(Se₂PtBu₂)₄ (2Se-Th-tBu). U(S₂PiPr₂)₄, 1S-U-iPr, could be made directly from UCl₄ and 4 equiv of KS₂PiPr₂. With (Se₂PiPr₂)1鈥?/sup>, using UCl₄ and 3 or 4 equiv of KSe₂PiPr₂ yielded the monochloride product U(Se₂PiPr₂)₃Cl (3Se-UiPr-Cl), but using UI₄(1,4-dioxane)₂ produced the homoleptic U(Se₂PiPr₂)₄ (1Se-U-iPr). Similarly, the reaction of UCl₄ with 4 equiv of KS₂PtBu₂ yielded U(S₂PtBu₂)₄ (2S-U-tBu), whereas the reaction with KSe₂PtBu₂ resulted in the formation of U(Se₂PtBu₂)₃Cl (4Se-UtBu-Cl). Using UI₄(1,4-dioxane)₂ and 4 equiv of KSe₂PtBu₂ with UCl₄ in acetonitrile yielded U(Se₂PtBu₂)₄ (2Se-U-tBu). Transmetalation reactions were investigated with complex 2Se-U-tBu and various CuX (X = Br, I) salts to yield U(Se₂PtBu₂)₃X (6Se-UtBu-Br and 7Se-UtBu-I) and 0.25 equiv of [Cu(Se₂PtBu₂)]₄ (8Se-Cu-tBu). Additionally, 2Se-U-tBu underwent transmetalation reactions with Hg₂F₂ and ZnCl₂ to yield U(Se₂PtBu₂)₃F (6) and U(Se₂PtBu₂)₃Cl (4Se-UtBu-Cl), respectively. The molecular structures were analyzed using 1H, 13C, 31P, and 77Se 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鈥搒elenium bonds over actinide鈥搒ulfur bonds.}