Tri- and Tetraphenylantimony 3,3,3-Trifluoropropanates: Synthesis and Structure
- 10 Downloads
Triphenylantimony bis(3,3,3-trifluoropropanate) (I) to be converted into tetraphenylantimony 3,3,3-trifluoropropanate (II) after additional treatment with pentaphenylantimony has been synthesized by the reaction between triphenylantimony and 3,3,3-trifluoropropanoic acid (HL) in the presence of tert-butyl hydroperoxide. The hydrolysis of complex I leads to the formation of µ2-oxo-bis(3,3,3-trifluoropropanatotriphenylantimony) (III). Complex II has also been synthesized from HL and pentaphenylantimony. The solvate Ph4SbOC(O)CH2CF3 ⋅ HOC(O)CH2CF3 (IV) has been isolated from the reaction mixture at an acid excess (2 : 1 mol/mol). According to X-ray diffraction data, the Sb atoms in complexes II–IV have differently distorted trigonal bipyramidal coordination. The СSbO axial angles in complexes II and IV are 173.29(7)° and 178.06(11)°, respectively. In a centrosymmetric molecule of complex III (the inversion center is the bridging oxygen atom), the OSbO angles are 175.64(6)°. The Sb–O and Sb–С bond lengths are 2.255(2) and 2.109(2)–2.167(2) Å in II; 1.8169(3), 2.045(2) and 2.065(2)–2.403(3) Å in III; 2.319(3) and 2.110(4)–2.168(3) Å in IV. The Sb⋅⋅⋅O intramolecular distances with the carbonyl oxygen atom (3.414(3) Å (II), 3.232(4) Å (III), 3.233(4) Å (IV)) are ~0.3–0.5 Å smaller than the sum of the antimony and oxygen van der Waals radii.
Keywords:triphenylantimony pentaphenylantimony carboxylate solvate X-ray diffraction analysis
The National South Ural State Research University is grateful to the Ministry of Education and Science of the Russian Federation for financial support (grant no. 4.6151.2017/8.9).
- 1.O. K. Sharutina and V. V. Sharutin, Molecular Structures of Organic Compounds of Antimony(V) (SUSU Press, Chelyabinsk, 2012) [in Russian].Google Scholar
- 4.T. C. Thepe, R. J. Garascia, M. A. Selvoski, et al., Ohio J. Sci., 77, 134 (1977).Google Scholar
- 5.V. V. Sharutin and V. S. Senchurin, Named Reactions in the Chemistry of Organoelement Chemistry (Chelyabinsk, 2011) [in Russian].Google Scholar
- 17.SMART and SAINT-Plus: Data Collection and Processing Software for the SMART System, Versions 5.0 (Bruker Madison, WI, 1998).Google Scholar
- 18.SHELXTL/PC: An Integrated System for Solving, Refining and Displaying Crystal Structures from Diffraction Data, Versions 5.10 (Bruker, Madison, WI, 1998).Google Scholar
- 20.A. V. Gushchin, Doctoral Dissertation in Chemistry (Nizhnii Novgorod, 1998).Google Scholar
- 21.V. V. Sharutin, V. S. Senchurin, O. K. Sharutina, et al., Russ. J. Gen. Chem. 66, 1750 (1996).Google Scholar
- 22.H. Schmidbaur and K. H. Mitschke, Angew. Chem., No. 83, 149 (1971). https://doi.org/10.1002/zaac.19713860204
- 24.M. N. Gibbons and D. B. Sowerby, J. Organomet. Chem. 555 271 (1998) doi org/Google Scholar