Reaction of tetraphenylphosphorus benzoate with benzoic acid

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The interaction of equimolar amounts of tetraphenylphosphorus benzoate and benzoic acid in benzene gave an adduct of tetraphenylphosphorus benzoate with benzoic acid (1) yielding 62% [color-less crystals with m.p. = 135 °C, soluble in aromatic hydrocarbons and polar organic solvents, which were identified by IR spectroscopy and X-ray diffraction analysis (XRD)]. In the IR spectrum of adduct 1, vi-brations of the P–CPh groups are observed as an intense band with an absorption frequency of 1438 cm–1, while the medium intensity bands at 995 and 1024 cm–1 correspond to deformation vibrations of the (P–CPh) bonds. The presence in the IR spectrum of the obtained complex of two intense absorption bands in the region of stretching vibrations of carbonyl groups (1639 and 1703 cm–1) indicates the presence of two nonequivalent carbonyl groups in the adduct. XRD was performed on a D8 QUEST Bruker diffrac-tometer. According to the X-ray diffraction data, adduct 1 [C76H62O8P2, M = 1165.2; triclinic syngony, space group P–1; cell parameters: a = 9.771(8) Å, b = 15.461(17) Å, c = 21.700(19) Å; α = 81.42(4)°, β = 81.34(3)°, γ = 74.07(4)°, V = 3096(5) Å3, Z = 2; ρcalc = 1.250 g/cm3; μ = 0.129 mm–1; F(000) = 1224.0; collection range by 2θ: 5.74–49.5°; –11 ≤ h ≤ 11, –18 ≤ k ≤ 18, –25 ≤ l ≤ 25; total reflections 56155; independent reflections 10540 (Rint = 0.1040); GOOF = 1.044; R1 = 0.0691] has an ionic structure and consists of two types of crystallographically independent tetraphenylphosphonium cations with a slightly distorted tetrahedral coordination of the phosphorus atom (the CPC angles vary within 106.28(16)−112.56(17)° (1a), 106.15(16)−112.03(17)° (1b), the P−C distances are 1.782(3)−1.800(4) Å (1a), 1.784(4)−1.794(3) Å (1b)] and two types of benzoate anions, in which the C−O bonds are: C(107)−O(5) 1,250(5) Å and C(107)−O(6) 1.227(5) Å (1a), C(87)−O(1) 1,297(5) Å and C(87)−O(2) 1.216(4) Å (1b). The bond angles in anions O(6)C(107)O(5) (1a) and O(2)C(87)O(1) (1b) are 125.9(4) and 123.6(4)°, respectively. It should be noted that the solvate molecules of benzoic acid are pairwise linked with the benzoate anions by hydrogen bonds C-COOH∙∙∙OC(O)Ph (1.375 and 1.395 Å). Complete tables of atomic coordinates, bond lengths and bond angles are deposited in Cambridge Structural Data Centre (no. 1983589; deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk/data_request/cif).

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Adduct, tetraphenylphosphorus benzoate, benzoic acid, synthesis, structure

Короткий адрес: https://sciup.org/147251995

IDR: 147251995   |   УДК: 546.185+547.53.024+548.312.2   |   DOI: 10.14529/chem250319