Abstract

The complexes \({\text{[P}}{{{\text{h}}}_{{\text{3}}}}{\text{PR]}}_{{\text{2}}}^{{\text{ + }}}\)[HfCl₆]^2–, where R = Et (I), CH₂C₆H₄CN-4 (II), or CH₂C₆H₄F-4 (III), have been synthesized by the reaction between hafnium tetrachloride and tetraorganylphosphonium chlorides in acetonitrile and structurally characterized. According to X-ray diffraction data, the phosphorus atoms in tetraorganylphosphonium cations have a distorted tetrahedral coordination: the CPC angles are 108.07(8)°–110.89(8)° (I), 105.0(3)°–113.8(3)° (II), and 99.5(4)°–115.7(4)° (III), and the P–С bond lengths are 1.7958(17)–1.8042(19) Å (I), 1.758(6)–1.834(6) Å (II), and 1.714(8)–1.930(10) Å (III). In the centrosymmetric octahedral anions [HfCl₆]^2– of complex I, the Hf–Cl distances are 2.4549(8)–2.4584(10) Å. In complexes II and III, the octahedral configuration of anions is distorted: the trans-ClHfCl angles are 177.23(13)°–180.00° and 177.73(9)°, 178.07(10)°, 178.84(9)°, respectively, and the Hf–Cl bonds are 2.3949(18)–2.4976(17) Å (II) and 2.411(2)–2.527(5) Å (III). The structural organization of crystals is formed by weak hydrogen bonds Cl⋅⋅⋅Н–С (2.75–2.92, 2.63–2.94, and 2.75–2.83 Å) between anions and cations.

中文翻译：

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Complex络合物$$ [{\\ mathbf {P}} {{{\ mathbf {h}}} _ {{\ mathbf {3}}}} {\ mathbf {PR}}] _ {{\ mathbf {2}} } ^ {+} $$ [HfCl 6] 2–，其中R = Et，CH 2 C 6 H 4 CN-4或CH 2 C 6 H 4 F-4：合成和结构

摘要

络合物\（{\文本{[P}} {{{\文本{H}}} _ {{\文本{3}}}} {\文本{PR]}} _ {{\文本{2}} } ^ {{\ text {+}}} \） [HfCl ₆ ] ^2–，其中R = Et（I），CH ₂ C ₆ H ₄ CN-4（II）或CH ₂ C ₆ H ₄ F-通过在乙腈中四氯化ha与四有机基phosph氯化物之间的反应合成了图4（III）。根据X射线衍射数据，四有机基phosph阳离子中的磷原子具有扭曲的四面体配位：CPC角为108.07（8）°–110.89（8）°（I），105.0（3）°–113.8（3）°（II）和99.5（4）°–115.7（4）°（III），并且P–С键长度为1.7958（17）–1.8042（19） Å（I），1.758（6）–1.834（6）Å（II）和1.714（8）–1.930（10）Å（III）。在配合物I的中心对称八面体阴离子[HfCl ₆ ] ^2–中，Hf–Cl距离为2.4549（8）–2.4584（10）Å。在配合物II和III中，阴离子的八面体构型发生了扭曲：反式ClHfCl角分别为177.23（13）°–180.00°和177.73（9）°，178.07（10）°，178.84（9）°，以及Hf-Cl键为2.3949（18）–2.4976（17）Å（II）和2.411（2）–2.527（5）Å（III）。晶体的结构组织是由阴离子和阳离子之间的弱氢键Cl⋅⋅⋅Н–С（2.75-2.92、2.63-2.94和2.75-2.83Å）形成的。