Oxidative addition reactions of triaryl antimony compounds with fluorinated carboxylic acids. Structure of reaction products[3-CH3C6H4)3SbOC(O)(CF2)3CF3]2O, [3-CH3C6H4)3SbOC(O)CF2CF2H]2O, [4-CH3C6H4)3SbOC(O)(CF2)3CF3]2O, [(3-FC6H4)3SbOC(O)CF2CF2H]2O

Abstract

Reaction of triarylantimony with fluorinated carboxylic acids [CF3(CF2)3C(O)OH and CHF2CF2C(O)OH] in the presence of tert-butyl hydroperoxide in ether led to triarylantimony oxo compounds [(3-MeC6H4)3SbOC(O)(CF2)3CF3]2O (1) and [(3-MeC6H4)3SbOC(O)CF2CHF2]2O (2), [(4-MeC6H4)3SbOC(O)(CF2)3CF3]2O (3), [(3-FC6H4)3SbOC(O)CF2CHF2]2O (4), the structure of which was proven by X-ray structural analysis (XRD). X-ray diffraction analysis of crystals 1-4 was performed on a D8 QUEST diffractometer from Bruker, the crystallographic characteristics of the unit cell of the compounds [1, triclinic space group P-1, a = 11.175(7), b = 19/597(9), c = 20.074(9) Å,  = 90.934(17), β = 96.79(2),  = 104.38(3), V = 4224(4) Å3, Z = 1, ρcalc = 1.571 g/cm3,  = 1.062 mm–1, F(000) = 1974.0; crystal size 0,22×0.09×0.05 mm, collection range data on 2θ, deg: 5.9254.4, index range –14 ≤ h ≤ 14, –25 ≤ k ≤ 25, –25 ≤ l ≤ 25, number of measured reflections 103747, number of independent reflections 18654, Rint = 0.1127, GOOF = 1.004, number of parameters 1050, R1 = 0.0535, wR2 = 0.1265; 2, space group triclinic P-1, a = 10.348(6), b = 15.131(10), c = 16.055(9) Å,  = 86.02(3), β = 71.70(2),  = 86.14(2), V = 2378(2) Å3, Z = 2, ρcalc = 1.531 g/cm3,  = 1.210 mm1, F(000) = 1092.0, crystal size 0.60.20.18 mm, data collection range for 2θ, deg: 5.6658.34, index range –14 ≤ h ≤ 14, –20 ≤ k ≤ 20, –21 ≤ l ≤ 21, number of measured reflections 95624, number of independent reflections 12765, Rint = 0.0470; GOOF = 1.053, number of parameters 574, R1 = 0.0374, wR2 = 0.0902; 3, space group tricli¬nic P-1, a = 11.761(5), b = 15.430(7), c = 16.785(11) Å,  = 101.96(3), β = 95.00(3),  = 106.726(18), V = 2819(3) Å3, Z = 2, ρcalc = 1.570 g/cm3,  = 1.061 mm1, F(000) = 1316.0, crystal size 0.50.30.09 mm, data collection range for 2θ, deg: 5.68454.32, index range: –15 ≤ h ≤ 15, –19 ≤ k ≤ 19, –21 ≤ l ≤ 21, number of measured reflections 69659, number of independent reflections 12413, Rint = 0.0561, GOOF = 1.068, number of parameters 700, R1 = 0.0461, wR2 = 0.1177; 4, space group triclinic P-1, a = 10.305(4), b = 15.152(10), c = 15.980(6) Å,  = 86.258(19), β = 71.792(13),  = 86.40(2), V = 2363(2) Å3, Z = 2, ρcalc = 1.574 g/cm3,  = 1.238 mm1, F(000) = 1092,0; crystal size 0.36×0.2×0.15 mm, data collection range for 2θ, deg: 5.6956.996; index range: –13 ≤ h ≤ 13, –20 ≤ k ≤ 20, –21 ≤ l ≤ 21, number of measured reflections 95211, number of independent reflections 11657, Rint = 0.0597; GOOF = 1.037, number of parameters 574, R1 = 0.0465, wR2 = 0.1139]. According to the X-ray diffraction data, the antimony atoms in molecules 1–4 have a distorted trigonal-bipyramidal coordination with the oxygen atoms of the carboxylate groups and the bridging oxygen atoms in axial positions; the aryl substituents are located in the equatorial plane. Crystal 1 contains two types of crystallographically independent molecules. The OSbO axial angles are 177.18(19)179.11(18)° in 1, 172.05(9), 178.21(10)° in 2, 174.76(16), 177.01(14)° in 3, 172.15(12), 178.31(13)° in 4. The SbOSb angles in two bridging molecules 1 are 142.8(2) and 179.999(1), similar angles in 2, 3, 4 are 143.63(13), 158.6(2), 143.91(17) respectively. The Sb–Obridge bond lengths [1.9336(10)–1.965(4) Å] are significantly shorter than the Sb–Oterm distances [2.207(7)–2.255(5) Å], which, in turn, are longer than the Sb–C bonds [2.045(6)–2.115(6) Å]. In molecules 1, intramolecular contacts are observed between the antimony atoms and the oxygen atoms of the carbonyl groups (the Sb∙∙∙O=C distances are 3.330–3.463 Å). Similar contacts in 2, 3, 4 are equal to 3.313 Å; 3.374 Å, 3.424 Å, and 3.323 Å, respectively. Complete tables of atomic coordinates, bond lengths and bond angles have been deposited with the Cambridge Crystallographic Data Centre (No. 2117717 (1), No. 2232674 (2), No. 2120417 (3), No. 2170735 (4); deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk/data_request/cif).