Abstract

Tetraarylantimony carboxylates Ph₄SbOC(O)R (R = CF₂Br (I), CF₂CF₂CF₃ (II)), (4‑MeC₆Н₄)₄SbOC(O)CF₂CF₃ (III), and (4-MeC₆Н₄)₄SbOC(O)CF₂CF₂CF₃ (IV) have been synthesized by the reaction between pentaarylantimony Ar₅Sb (Ar = Ph, 4-MeC₆H₄) and fluorine-containing carboxylic acids. Despite an excess amount of carboxylic acid in the reaction mixture, it does not form any solvates Ar₄SbOC(O)R ⋅ HOC(O)R with tetraarylantimony carboxylates. X-ray diffraction shows that the Sb atoms in complexes I–IV have differently distorted trigonal bipyramidal coordination. Crystals of complexes III and IV contain two types of crystallographically independent molecules. The axial СSbO angles in complexes I, II, III, and IV are 175.32(14)°, 178.87(8)°, 178.56(13)° and 178.33(10)°, 178.16(13)°, and 179.58(15)°, respectively. The Sb–O and Sb–С bond lengths are 2.333(3) and 2.106(4)–2.151(5) Å in I, 2.340(2) and 2.101(2)–2.154(3) Å in II, 2.364(3), 2.411(3), and 2.096(4)–2.159(4) Å in III, and 2.376(3), 2.367(3), and 2.105(4)–2.161(4) Å in IV. The intramolecular Sb⋅⋅⋅O distances with the carbonyl oxygen atom are 3.506(4) Å (I), 3.517(6) Å (II), 3.565(6) Å (III), and 3.527(6) Å (IV), being ~0.2 Å smaller than the sum of Sb and O van der Waals radii. The second carbonyl oxygen atoms in crystals of complexes III and IV do not participate in the coordination with the central metal atom.

中文翻译：

---

含氟四芳基锑羧酸盐：合成与结构

摘要

Tetraarylantimony羧酸博士₄ SBOC（O）R（R = CF ₂ Br（上我），CF ₂ CF ₂ CF ₃（II）），（4-MEC ₆ Н ₄）₄ SBOC（O）CF ₂ CF ₃（III） ，和（4-MEC ₆ Н ₄）₄ SBOC（O）CF ₂ CF ₂ CF ₃（IV）已经由pentaarylantimony氩之间的反应合成₅的Sb（AR = PH，4-MEC ₆ ħ ₄）和含氟羧酸。尽管反应混合物中羧酸的量过多，但它不会与四芳基锑羧酸盐形成任何溶剂化物Ar ₄ SbOC（O）R⋅HOC（O）R。X射线衍射表明，配合物I – IV中的Sb原子具有不同的畸变三角双锥体配位。配合物III和IV的晶体包含两种晶体学独立的分子。配合物I，II，III和IV的轴向СSbO角分别为175.32（14）°，178.87（8）°，178.56（13）°和178.33（10）°，178.16（13）°和179.58（15）°。I中的Sb-O和Sb-С键长分别为2.333（3）和2.106（4）-2.151（5）Å，II中为2.340（2）和2.101（2）-2.154（3）Å，II，2.364（3） ），2.411（3），和2.096（4）-2.159（4）在III，和2.376（3），2.367（3），和2.105（4）-2.161（4）在IV。分子内Sb⋅⋅⋅O与羰基氧原子的距离为3.506（4）Å（I），3.517（6）Å（II），3.565（6）Å（III）和3.527（6）Å（IV）比Sb和O van der Waals半径的总和小〜0.2Å。配合物III和III晶体中的第二个羰基氧原子四，不参与与中心金属原子的配位。