Thorium Compounds with Bonds to Sulfur or Selenium: Synthesis, Structure, and Thermolysis

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• 作者：David Rehe ; Anna Y. Kornienko ; Thomas J. Emge ; John G. Brennan
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：July 18, 2016
• 年：2016
• 卷：55
• 期：14
• 页码：6961-6967
• 全文大小：440K
• 年卷期：0
• ISSN：1520-510X

文摘

Thorium chalcogenolates Th(ER)₄ (E = S, Se; R = Ph, C₆F₅) form pyridine complexes with a variety of coordination numbers. Four compounds, (py)₄Th(SPh)₄, (py)₃Th(SePh)₄, (py)₃Th(SC₆F₅)₄, and (py)₄Th(SeC₆F₅)₄, have been isolated and characterized by spectroscopic methods and low-temperature single crystal X-ray diffraction. Two of the products, (py)₄Th(SPh)₄ and (py)₄Th(SeC₆F₅)₄, have classic eight coordinate A₄B₄ square-antiprism geometries. The SePh compound is the only seven coordinate (4Se, 3N) product, and the fluorinated thiolate is distinctive in that the structure contains two dative interactions between Th and fluoride, to give a nine coordinate (3N, 4S, 2F) structure. The EPh compounds decompose thermally to give ThE₂ and EPh₂, while the fluorinated compounds give primarily ThF₄, E₂(C₆F₅)₂, and E(C₆F₅)₂.