Reactions of triphenylantimony with difluorobromoacetic acid in the presence of tert-butyl hydroperoxide in ether

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Oxobis(difluorobromoacetatotriphenylantimony) [Ph3SbOC(O)CF2Br]2O (1) was synthesized by interaction of equimolar amounts of triphenylantimony and difluorobromoacetic acid in the presence of tertbutyl hydroperoxide in ether at room temperature. Under similar conditions at the molar ratio of 1:2:1, the corresponding triphenylantimony dicarboxylate Ph3Sb[OC(O)CF2Br]2 (2) was formed. The structure of complexes 1 and 2 is proven by Xray diffraction. Crystallographic characteristics of 1 C40H30Br2F4O5Sb2, M = 1069.96; triclinic syngony, space group P1; cell parameters: a = 9.899(5) Å, b = 15/325(6) Å, c = 22.083(10) Å;  = 71.858(13), β = 85.93(3),  = 71.405(19), V = 3016(2) Å3, Z = 1.5; calc = 1.767 g/cm3;  = 3.391 mm–1; F(000) = 1554.0; region collection at 2: 5.67–56.752; –13 ≤ h ≤ 13, –20 ≤ k ≤ 20, –29 ≤ l ≤ 29; total reflections 106273; independent reflections 15000 (Rint = 0.0556); GOOF = 1.019; Rfactor = 0.0595]; 2 [C22H15Br2F4O4Sb, M = 700.92; monoclinic syngony, space group C2/c; cell parameters: a = 18.118(16) Å, b = 10.305(6) Å, c = 14.431(11) Å; β = 108.94(6), V = 2548(3) Å3, Z = 4; calc = 1.829 g/cm3;  = 4.272 mm–1; F(000) = 1348.0; collection area by 2: 5.898–56.99; –24 ≤ h ≤ 24, –13 ≤ k ≤ 13, –19 ≤ l ≤ 19; total reflections 67806; independent reflections 3215 (Rint = 0.0731); GOOF = 1.556; Rfactor = 0.1051]. From the Xray diffraction data it follows that crystal 1 consists of two types of binuclear bridging molecules A and B, one of which is centrosymmetric (the inversion center is the bridging oxygen atom) and has a linear fragment Sb(1)O(1)Sb(1), in the second molecule the analogous angle Sb(2)O(4)Sb(3) is 141.6(2)°, while the lengths of the SbObrid bonds [1.9368(9)1.971(4) Å] are significantly shorter than the terminal SbOterm bonds (2.209(5)2.233(5) Å). The antimony atoms in 1 and 2 have a distorted trigonalbipyramidal coordination with the oxygen atoms in axial positions [OSbO 176.7(5) Å for 2] and equatorial SbC bond lengths 2.079(4)2.108(6) Å. In the linear centrosymmetric molecule 1A there are coordination bonds of the central metal atom with the carbonyl oxygen atom [Sb∙∙∙O=C 3,450(9) Å], while in the isocurved molecule 1B such coordination is observed only for one carbonyl group [3.302(8) Å]. The antimony atoms in the centrosymmetric molecule 2 (the inversion center is the antimony atom) have a distorted trigonalbipyramidal coordination with the oxygen atoms of the carboxyl groups in the axial positions [OSbO 176.7(5); SbO 2.100(11) Å] and the equatorial phenyl ligands [SbC 2.097(16), 2.110(6) Å]. Due to the bidentate nature of the carboxylate ligands in structure 2, there are intramolecular contacts between the Sb and O atoms of the carbonyl groups [3.174(7) Å]. The formation of intramolecular contacts Sb⋅⋅⋅O(=C) in 2 occurs within two CSbC equatorial angles, as a result, the CSbC equatorial angles differ slightly from each other [117.0(5), 121.5(2), 121.5(2)]. Complete tables of atomic coordinates, bond lengths, and valence angles of compounds 1 and 2 have been deposited at the Cambridge Crystallographic Data Centre (CCDC 2217059 and 2084130; deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk)

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Triphenylantimony, difluorobromoacetic acid, tert-butyl hydroperoxide, μ2-oxobis[(difluorobromoacetato)triphenylantimony], bis(difluorobromoacetato)triphenylantimony, synthesis, structural features

Короткий адрес: https://sciup.org/147251985

IDR: 147251985   |   УДК: 546.865+547.53.024+546.21+546.16+548.539.26+548.312.5   |   DOI: 10.14529/chem250308