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Hafnium Complexes \([{\mathbf{P}}{{{\mathbf{h}}}_{{\mathbf{3}}}}{\mathbf{PR}}]_{{\mathbf{2}}}^{ + }\)[HfCl6]2–, where R = Et, CH2C6H4CN-4, or CH2C6H4F-4: Synthesis and Structure

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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.

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Sharutin, V.V., Sharutina, O.K. & Lobanova, E.V. Hafnium Complexes \([{\mathbf{P}}{{{\mathbf{h}}}_{{\mathbf{3}}}}{\mathbf{PR}}]_{{\mathbf{2}}}^{ + }\)[HfCl6]2–, where R = Et, CH2C6H4CN-4, or CH2C6H4F-4: Synthesis and Structure. Russ. J. Inorg. Chem. 65, 870–873 (2020). https://doi.org/10.1134/S0036023620060200

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