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Calorimetric Study of Triphenylbismuth Dimethacrylate Ph3Bi(O2CCMeCH2)2 Irina A. Letyanina,†,‡ Alexey V. Markin,*,† Alexey V. Gushchin,† Natalia N. Smirnova,† Marina N. Klimova,† and Olga S. Kalistratova† †

Lobachevsky State University of Nizhni Novgorod, 23/5 Prospekt Gagarina, 603950 Nizhni Novgorod, Russian Federation Saint Petersburg State University, 26 Universitetskiy Prospect, Peterhof, 198504 Saint Petersburg, Russia

‡

S Supporting Information *

ABSTRACT: In the present research, the heat capacities of triphenylbismuth dimethacrylate Ph3Bi(O2CCMeCH2)2 were measured between T = 5.3 and 330 K with the precision adiabatic vacuum calorimeter and from T = 310 to 420 K with the differential scanning calorimeter. There revealed a reproducible anomaly from 150 to 170 K caused by structural changes in the crystal lattice, and intensive exothermic transition over the range from T = 385 to 420 K caused by the reductive decomposition with the polymerization of the sample under study. The experimental results were used to calculate the standard (p = 0.1 MPa) thermodynamic functions (heat capacity Cop,m, enthalpy Hom(T) − Hom(0), entropy Som(T), and Gibbs energy Φom(T) of crystalline triphenylbismuth dimethacrylate from T → 0 to 385 K. The standard entropy of formation at T = 298.15 K was calculated for the compound under study in the crystalline state. Obtained for Ph3Bi(O2CCMeCH2)2 results were compared with ones for Ph3Sb(O2CCMeCH2)2.

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from T → 0 to 385 K, and the standard entropy of formation, ΔfSom at T = 298.15 K for crystalline Ph3Bi(O2CCMeCH2)2.

INTRODUCTION Organic derivatives of pentavalent bismuth, their synthesis, and investigation of their properties are of considerable interest because they find an application in different fields of practice, for example, as reagents and catalysts in fine organic synthesis, pharmaceutical composition, biocides, and fungicides. Some researchers note that bismuth and bismuth compounds are the least toxic among the heavy metals,1,2 and it can lead to increasing their usage in the pharmaceutical and cosmetic industry. In organic chemistry, triarylbismuth(V) derivatives find a use in Heck-type C-arylation reaction to form the cross-coupling products.3,4 The physicochemical investigation of these types of compounds is an actual task. Previously, we focused on the thermodynamic properties of the organic derivatives of pentavalent antimony (pentaphenylantimony Ph5Sb,5 tetraphenylantimony benzophenoneoxymate Ph4SbONCPh2,6 tetraphenylantimony acetophenoneoxymate Ph4SbONCPhMe,7 triphenylantimony bis(acetophenoneoxymate) Ph3Sb(ONCPhMe)2,8,9 triphenylantimony diacrylate Ph3Sb(O2CCHCH2)2,10 triphenylantimony dimethacrylate Ph3Sb(O2CCMeCH2)2,11 and triphenylantimony bis(1-adamantanecarboxylate) Ph3Sb[OC(O)C10H15]212). The present paper is devoted to the calorimetric study of triphenylbismuth dimethacrylate Ph3Bi(O2CCMeCH2)2 over the temperature range from T = 5.3 to 420 K, detection of possible physical transitions, the calculation of the standard thermodynamic functions, namely, Cop,m, Hom(T) − Hom(0), Som(T), and Φom(T) © XXXX American Chemical Society

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EXPERIMENTAL SECTION

Synthesis and Characterization of Triphenylbismuth Dimethacrylate Ph3Bi(O2CCMeCH2)2. Triphenylbismuth dimethacrylate Ph3Bi(O2CCMeCH2)2 was obtained by the method of oxidative addition from triphenylbismuth, hydrogen peroxide, and an excess of methacrylic acid, mixed in the 1:1:3 ratio, respectively13 Ph3Bi + 2CH 2 = CMeCOOH + H 2O2 → Ph3Bi(O2 CCMeCH 2)2 + 2H 2O

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Diethyl ether was used as solvent. The reaction was carrying out at T = 278 K for 38 h. Yield of target product was 60% after recrystallization from the mixture of chloroform and hexane. The compound under study was a white crystalline substance, air and moisture stable, well soluble in chloroform, tetrahydrofuran, methyl methacrylate, styrene, benzene, and sparingly soluble in hexane and isopropyl alcohol. Good solubility in styrene and methyl methacrylate makes the product promising in order to obtain bismuth-containing polymers. Received: December 3, 2015 Accepted: June 19, 2016

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DOI: 10.1021/acs.jced.5b01032 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

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Figure 1. IR spectrum of triphenylbismuth dimethacrylate Ph3Bi(O2CCMeCH2)2.

(Japan) in a potassium bromide pellet containing 1% of the investigated compound. In an IR spectrum of the product (Figure 1), the medium absorption band, corresponding to the stretching vibrations of Bi−C bonds, was at 679 cm−1. The band at 449 cm−1 belonged to the stretching vibration frequency of Bi−O bonds. The strong bands with maxima at 1362 and 1559 cm−1 were related to the asymmetric and symmetric absorption vibration frequencies of COO groups, respectively. The band with maximum at 3045 cm−1 belonged to the stretching vibration frequency of C−H bonds of phenyl groups. The wavenumbers of the noted vibrations were close to similar values for triphenylantimony dimethacrylate.15 The 1H and 13C NMR spectra were recorded on the NMRspectrometer Ajilent DD2 400 in deuterochloroform. Decoding and modeling of spectra were performed using the program MestReNova. In 1H NMR spectrum of Ph3Bi(O2CCMe CH2)2 (Figure 2) the multiplet of protons of Ph groups was observed in a weak field (δ 7.4−8.2 ppm, I = 14.8, calcd. 15.0); two singlets of CH2 protons were observed in a stronger field (5.9 and 5.3 ppm, I = 2.02 and 2.03, calcd. 2.00); the singlet of CH3 protons was observed in a strong field (1.8 ppm, I = 6.00, calcd. 6.00). The chemical shift values of these proton groups

The structure and the composition of the compound under study were investigated by the methods of elemental analysis, 1 H, 13C NMR, and IR spectroscopy. Elemental analysis was carried out using the manual express gravimetric method based on pyrolytic burning of a substance in a quartz tube in oxygen flow. This method allows determination of carbon and hydrogen contents, as well as bismuth by the remainder of bismuth(III) oxide. The standard uncertainties for C, H, and Bi obtained with the manual express gravimetric method were u(C) = 0.15, u(H) = 0.09, and u(Bi) = 0.5. Because the uncertainty for Bi was quite great, the method of titrimetric bismuth determination was developed;13 the standard uncertainty obtained with this method was u(Bi) = 0.2. The molar mass of Ph3Bi(O2CCMeCH2)2 was calculated from the International Union of Pure and Applied Chemistry (IUPAC) table of atomic weights.14 The elemental analysis data were in good agreement with the calculated ones. Found, %: C 51.00; H 4.12; Bi 35.00 (express gravimetric method) and 34.23 (titrimetric method). Calculated for C26H25O4Bi, %: C 51.13; H 4.13; Bi 34.25. The IR absorption spectra were recorded on the IRspectrometer IR Prestige-21 of the company Shimadzu B



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Figure 2. 1H NMR spectrum of triphenylbismuth dimethacrylate Ph3Bi(O2CCMeCH2)2.

ur(Cop,m) = 0.02 at T < 15 K, ur(Cop,m) = 0.005 over the temperature range of 15 to 40 K, and ur(Cop,m) = 0.002 between T > 40 K. The sample mass was 0.7337 g, and 220 experimental Cop,m values were obtained in the following three series of experiments: over the range 5.31−89.33 K in the first series, from 80.44 to 331.76 K in the second series, and from 139.89 to 182.47 K in the third series (the third series was done to confirm the observed within this temperature range anomaly) (Table 2). In the whole temperature range, the heat capacity of the samples was (25−50) % of the total heat capacity of the calorimetric ampule with the substance. Differential Scanning Calorimetry. The differential scanning calorimeter20,21 (model: DSC 204 F1 Phoenix, Netzsch, Germany) was used to measure the heat capacities of the compound under study over the range from T = 310 to 420 K. The reliability of the calorimeter was verified by melting of n-heptane, mercury, tin, lead, bismuth, and zinc. The heat capacity was determined by the “Ratio method” with corundum used as a standard reference sample. The technique for determining of Cop,m according to the data of DSC measurements is described in detail in20,21 and the Netzsch Software Proteus. The relative standard uncertainty for heat capacities was ur(Cop,m) = 0.02. The measurement procedure allowed to determine the temperatures of transformations with the standard uncertainty u(T) = 0.5 K, and the enthalpies of transitions with the relative standard uncertainty ur(ΔtrH°) = 0.01. The values of the transitions’ characteristics were

are close to similar values for triphenylantimony dimethacrylate.15 In 13C NMR spectrum of the compound under study (Figure 3), the signals of carbon atoms of phenyl groups (130.5; 130.9; 133.8; 160.4 ppm) and methacrylate groups (19.0; 122.9; 139.1; 173.5 ppm) were present. The content of the main substance in the samples was estimated to be not less 0.99 mole fraction. The impurities were not identified but we estimated that their amount did not influence the accuracy of the thermodynamic investigations. The information for the studied sample is listed in Table 1. The thermal stability of the sample under study was investigated with the microbalance TG 209 F1 Iris (Netzsch, Getrmany). The thermal microbalance allowed to fix the mass change within standard uncertainty u(m) = 10−5 g. The measurement was performed with a heating rate of 10 K·min−1 in argon atmosphere. The measuring technique of the TG analysis was standard, according to the Netzsch Software Proteus. The significant mass lost was observed since T = 385 K. Adiabatic Calorimetry. Heat capacities of Ph 3 Bi(O2CCMeCH2)2 were measured over the range from T = 5.31 to 331.76 K in a BKT-3.0 fully automatic adiabatic vacuum calorimeter. Liquid helium and nitrogen were used as cooling agents. The calorimeter design and measurement procedure are similar to those reported elsewhere.16,17 The calorimeter was tested by measuring the heat capacity of special purity copper, standard synthetic corundum and K-3 benzoic acid.18,19 The relative uncertainties in heat capacity measurements were C



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Figure 3. 13C NMR spectrum of triphenylbismuth dimethacrylate Ph3Bi(O2CCMeCH2)2.

Table 1. Sample Information chemical name

source

state

mole fraction purity

analysis method

Ph3Bi(O2CCMeCH2)2

present work

powder

0.99

elemental analysis, 1H, 13C NMR, IR spectroscopy, thermogravimetric analysis 7

evaluated according to the standard Netzsch Software Proteus procedure. The heating rate was 5 K min−1, and the measurements were carried out in argon atmosphere. The o obtained Cp,m experimental data are presented in the Supporting Information (Table S1).

o Cp,m =

i=0

RESULTS AND DISCUSSION Heat Capacity. The experimental data of heat capacity of triphenylbismuth dimethacrylate over the temperature range from 5 to 420 K and the smoothed plot Cop,m = f(T) are illustrated in Figure 4. The experimental points of Cop,m in the temperature range between T = 5.3 and 150 K and from T = 170 to 385 K were fitted by means of the least-squares method and the polynomial equations of the Cop,m versus temperature for the ranges from T = 5.3 to 30 K and from T = 20 to 90 K were 13

⎡ ⎛ T ⎞⎤i ⎟⎥ 30 ⎠⎦

∑ Ai⎢⎣ln⎜⎝ i=0

(3)

The relative standard uncertainty for the heat capacities was ur(Cop,m) = 0.005 in the temperature range of 5.3 to 90 K, ur(Cop,m) = 0.0025 between T = 82 to 330 K, and ur(Cop,m) = 0.006 between T = 310 to 385 K. Over the ranges from T = 150 to 170 K, a phase transition is observed. It is a λ-transition22 that looks like a positive deviation of the experimental Cop,m values from a normal trend of the curve of temperature dependence of the heat capacity. This transition was reproduced every time on cooling and heating of the substance. We estimated the thermodynamic characteristics of the transition, viz. the temperature interval T = 150 to 170 K, the enthalpy ΔtrHom = 77.1 J·mol−1, standard uncertainty u(ΔtrHom) = 19.7 J·mol−1, and the entropy ΔtrSom = 0.482 J·mol−1·K−1, standard uncertainty u(ΔtrSom) = 0.123 J·mol−1·K−1. ΔtrHom and ΔtrSom were calculated from the area between anomalous and normal trends of the curves Cop.m = f(T) and Cop.m = f(ln T) respectively. It is should be noted that similar transition was revealed for triphenylantimony dimethacrylate11 over the temperature range from T = 150 to 167 K.

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o ln Cp,m =

⎛ T ⎞i ⎟ 30 ⎠

∑ Ai⎜⎝

(2)

and for the ranges from T = 82 to 150 K, from T = 170 to 330 K, and from T = 310 to 385 K were D



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Table 2. Experimental Molar Heat Capacity Cop,m of Triphenylbismuth Dimethacrylate Ph3Bi(O2CCMeCH2)2 (M = 610.42 g·mol−1)a,b at Pressure p = 0.1 MPa Series 1

Series 1

Series 2

Series 2

T (K)

Cop,m J·mol−1·K−1

T (K)


T (K)


T (K)


5.31 5.50 5.69 5.89 6.13 6.43 6.72 7.00 7.61 7.92 8.21 8.47 8.74 9.01 9.31 9.60 9.89 10.18 10.46 10.74 11.02 11.29 11.57 11.86 12.14 12.60 13.23 13.87 14.50 15.14 15.77 16.42 17.07 17.75 18.43 19.13 19.85 20.71 21.55 22.40 23.27 24.15 25.07 25.99 26.94 27.91 28.90 29.91 30.94 31.98 33.05 34.13 35.22 36.33 37.46 38.61

2.67 2.97 3.31 3.60 4.00 4.63 5.14 5.83 7.13 7.83 8.53 9.17 9.71 10.4 11.1 11.9 12.5 13.2 14.1 15.0 15.7 16.4 17.3 18.1 18.8 19.8 21.4 23.1 25.1 27.14 29.20 31.34 33.40 35.37 37.14 39.13 41.30 44.22 46.93 50.08 52.85 56.07 58.64 61.38 64.30 67.40 70.60 73.70 77.40 80.82 84.60 88.08 91.41 94.56 97.88 101.6

80.44 82.34 84.24 86.15 88.06 89.97 91.89 93.80 95.66 97.64 99.56 101.48 103.41 105.33 107.25 109.18 111.10 113.02 114.94 116.87 118.79 120.72 122.64 124.56 126.48 128.40 130.32 132.24 134.15 136.06 137.98 139.89 141.78 143.69 145.59 147.50 149.39 151.76 154.53 154.60 157.36 160.17 162.98 165.78 168.58 171.37 174.16 176.94 179.71 182.47 185.23 187.98 190.70 193.45 196.12 198.84

209.4 213.7 217.7 221.8 225.3 229.2 233.1 236.8 240.4 244.4 247.5 251.3 254.6 257.5 261.1 264.4 267.1 270.8 273.9 276.8 279.4 282.5 286.0 289.4 292.2 295.5 298.6 301.7 304.9 307.6 310.6 313.5 316.5 319.6 322.2 324.4 327.6 332.0 339.3 339.5 345.2 350.0 355.2 356.4 356.9 361.1 365.1 369.0 373.3 377.6 381.3 385.2 390.0 393.8 397.3 402.3

39.77 40.95 42.14 43.35 44.56 45.79 47.02 48.27 49.52 50.78 52.04 53.32 54.60 55.89 57.18 58.48 59.80 61.11 62.43 63.75 65.07 66.41 67.74 69.08 70.43 71.77 73.10 74.43 75.77 77.10 78.44 79.79 81.14 82.50 83.65 85.07 86.57 87.92 89.33

105.1 108.6 112.0 115.4 119.7 123.5 127.4 130.9 134.5 137.9 141.2 144.6 148.0 151.3 154.6 158.3 161.7 165.1 168.3 171.7 174.7 177.8 181.0 184.1 187.2 190.2 193.3 196.3 199.3 202.0 204.9 207.7 210.8 213.9 216.2 219.4 222.5 225.1 227.8

201.54 204.24 206.93 209.62 212.31 215.00 217.69 220.38 223.07 225.75 228.44 231.12 233.81 236.49 239.78 242.50 245.23 247.95 250.68 253.44 256.17 258.91 261.65 264.38 267.13 269.87 272.61 275.35 278.09 280.83 283.57 286.31 289.04 291.78 294.51 297.40 300.17 302.94 305.64 308.25 310.82 313.33 315.79 318.21 320.26 322.58 324.90 327.21 329.49 331.76

406.8 410.5 414.6 418.8 424.2 428.1 432.0 436.0 440.2 444.7 448.9 452.7 456.8 460.5 465.8 470.7 474.8 477.9 482.7 487.1 491.7 495.5 499.2 503.3 507.9 511.7 517.6 521.0 526.0 530.7 535.5 540.7 545.2 550.5 555.4 560.2 564.0 568.2 573.5 577.7 581.1 585.3 588.7 592.5 596.3 600.0 604.3 607.7 612.7 617.5

a The standard uncertainty for temperature u(T) = 0.01 K. The standard uncertainty for pressure u(p) = 10 kPa. The relative standard uncertainty for heat capacity ur(Cop,m) = 0.02 in the temperature range from T = 5 to 15 K, ur(Cop,m) = 0.005 between T = 15 to 40 K, ur(Cop,m) = 0.002 in the temperature range from T = 40 to 330 K. bData obtained with the adiabatic vacuum calorimeter.

E



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Figure 4. Temperature dependences of experimental molar heat capacity of triphenylbismuth dimethacrylate Ph3Bi(O2CCMeCH2)2.

Figure 5. Temperature dependences of molar heat capacities of triphenylbismuth dimethacrylate (1) and triphenylantimony dimethacrylate11 (2).

The essential decreasing of heat capacity was observed from T = 385 K, where the second transition begins. The transition was not reproduced on subsequent cooling and heating. The sample of triphenylbismuth dimethacrylate was additionally studied with the methods of infrared spectroscopy. The analysis showed the decrease of the quantity of double bonds after heating the sample up to T > 450 K that was evidence of the

beginning of the polymerization of the compound under study. Also, the thermogravimetric analysis of Ph3Bi(O2CCMe CH2)2 showed a considerable mass loss over the temperature range of the transition. It was ∼2% to T = 385 K. Thus, the observation for triphenylbismuth dimethacrylate second transition was probably caused by the reductive decomposition with the polymerization. F



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Table 3. Smoothed Molar Heat Capacity and Thermodynamic Functions of Crystalline Triphenylbismuth Dimethacrylate Ph3Bi(O2CCMeCH2)2 (M = 610.42 g·mol−1) at Pressure p = 0.1 MPaa T (K)


Hom(T) − Hom(0) kJ·mol−1

Som(T) J·mol−1·K−1

−Φom(T) kJ·mol−1b

5 10 15 20 25 30 35 40 45 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 273.15 280 290 298.15 300 310 320 330 340 350 360 370 380 385

2.21 13.0 26.8 41.89 58.51 74.21 90.66 105.6 121.0 135.7 162.0 186.4 208.3 229.3 248.4 265.7 281.7 298.0 313.9 328.7 349.7 358.9 373.8 388.4 403.8 419.8 435.8 451.3 466.4 481.3 496.7 512.8 518.0 529.7 546.9 560.8 563.9 580.1 595.7 612 628 646 659 665 671 679

0.00280 0.0382 0.137 0.3086 0.5598 0.8906 1.303 1.794 2.361 3.003 4.494 6.238 8.212 10.40 12.79 15.36 18.10 21.00 24.06 27.27 30.67 34.22 37.89 41.70 45.66 49.78 54.05 58.49 63.08 67.82 72.71 77.75 79.38 82.97 88.35 92.86 93.90 99.62 105.5 112 118 124 131 137 144 147

0.739 5.23 13.0 22.81 33.95 45.97 58.66 71.75 85.08 98.60 125.7 152.6 178.9 204.6 229.8 254.3 278.1 301.3 324.0 346.1 368.0 389.6 410.5 431.1 451.4 471.5 491.4 511.1 530.7 550.0 569.2 588.2 594.2 607.2 626.1 641.4 644.9 663.7 682.3 701 719 738 756 774 792 801

0.000925 0.0140 0.0586 0.1476 0.2889 0.4885 0.7497 1.076 1.468 1.927 3.049 4.440 6.098 8.016 10.19 12.61 15.27 18.17 21.30 24.65 28.22 32.01 36.01 40.22 44.63 49.24 54.06 59.07 64.28 69.69 75.28 81.07 82.93 87.05 93.21 98.38 99.57 106.1 112.8 120 127 134 142 149 157 161

a

The standard uncertainty for temperature u(T) = 0.01 K in the temperature range from T = 5 to 330 K, and u(T) = 0.5 K in the interval between T = 320 and 385 K. The standard uncertainty for pressure u(p) = 10 kPa. Relative expanded uncertainties for the heat capacity Ur(Cop,m) are 0.04, 0.01, 0.004, and 0.04; Ur(Hom(T) − Hom(0)) are 0.046, 0.016, 0.005, and 0.046; Ur(Som(T)) are 0.046, 0.016, 0.005, and 0.046; Ur(Φom(T)) are 0.05, 0.02, 0.01, and 0.05 in the ranges 5 ≤ T/K ≤ 15, 15 ≤ T/K ≤ 40, 40 ≤ T/K ≤ 330, and 330 ≤ T/K ≤ 385, respectively, for 0.95 level of confidence (k ≈ 2). bΦom(T) = [Hom(T) − Hom(0)] − T·Som(T)

T = 150 to 170 K, for both compounds we have revealed the anomaly, which can be explained by the structure changes in the crystals of the compounds. The main difference is observed at high temperatures; the sample of Ph3Bi(O2CCMeCH2)2 begins to polymerize at T = 385 K but Ph3Sb(O2CCMe CH2)2 begins to melt at T = 400 K, and both processes are accompanied by the decomposition of the samples.

The comparison of heat capacities for Ph3Bi(O2CCMe CH2)2 and Ph3Sb(O2CCMeCH2)211 (Figure 5) shows that the heat capacity values are similar within the ranges where the physical transitions have not been revealed and the difference does not exceed 3%. It is explained by close topology and likeness of the structures of the compounds and weak influence of the central atom on the heat capacity. Over the range from G



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Funding

Standard Thermodynamic Functions. To calculate the standard thermodynamic functions of crystalline Ph3Bi(O2CCMeCH2)2 its heat capacity values were extrapolated from the temperature of the measurement beginning as T → 0 with the Debye law in the low-temperature limit23 ⎛θ ⎞ o Cp,m = nD⎜ D ⎟ ⎝T ⎠

The reported study was supported the Ministry of Education and Science of the Russian Federation (Contract No. 4.1275.2014/K) and by the Russian Foundation of Basic Research (research projects No. 14-03-31038 mol_a and No. 14-03-31625 mol_a). I.L. is grateful to St. Petersburg State University for Research Fellow Grant (12.50.1564.2013).

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Notes

The authors declare no competing financial interest.

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where n is the number of degrees of freedom, D is the Debye function, and θD refers to the Debye characteristic temperature. The parameters of n = 6 and θD = 60.25 K are specially selected. Using these parameters, eq 4 describes the experimental heat capacities of the compound within the range of T = 6−12 K with the error of ±1.05%. In calculating the functions, it was assumed that eq 4 reproduced the Cop,m values of Ph3Bi(O2CCMeCH2)2 at T < 6 K with the same error. The calculation of enthalpy and entropy was made by the numerical integration of heat capacity. These calculations for selected temperatures are given in the Table 3. The Gibbs energy was calculated with Gibbs−Helmholtz equation from the enthalpies and entropies at the corresponding temperatures.24 The absolute entropies of the compound under study (Table 3) and the corresponding elemental substances, C (gr),25 H2 (g),25 O2 (g),25 Bi (cr),26 were used to calculate the standard entropy of formation of Ph3Bi(O2CCMeCH2)2 in crystalline state at T = 298.15 K: ΔfSom (298.15, Ph3Bi(O2CCMeCH2)2, cr) = −1608.5 ± 5.6 J·mol−1·K−1. Obtained values fit the equations

(1) Suzuki, H.; Komatsu, N.; Ogawa, T.; Murafuji, T.; Ikegami, T.; Matano, Y. Organobismuth Chemistry; Elsevier Science: Amsterdam, 2001. (2) Ollevier, T. Bismuth-Mediated Organic Reactions; Springer Verlag: Berlin, 2012. (3) Moiseev, D. V.; Malysheva, Yu.B.; Shavyrin, A. S.; Kurskii, Yu.A.; Gushchin, A. V. Study of Homo- and Cross-Coupling Competition in the Reaction of Triarylbismuth(V) Dicarboxylates with Methyl Acrylate in the Presence of a Palladium Catalyst. J. Organomet. Chem. 2005, 690, 3652−3663. (4) Malysheva, Yu.B.; Gushchin, A. V.; Mei, Y.; Lu, Y.; Ballauff, M.; Proch, S.; Kempe, R. C−C Coupling Reaction of Triphenylbismuth(V) Derivatives and Olefins in the Presence of Palladium Nanoparticles Immobilized in Spherical Polyelectrolyte Brushes. Eur. J. Inorg. Chem. 2008, 2008, 379−383. (5) Smirnova, N. N.; Letyanina, I. A.; Larina, V. N.; Markin, A. V.; Sharutin, V. V.; Senchurin, V. S. Thermodynamic Properties of Pentaphenylantimony Ph5Sb over the Range from T → 0 to 400 K. J. Chem. Thermodyn. 2009, 41, 46−50. (6) Smirnova, N. N.; Letyanina, I. A.; Markin, A. V.; Larina, V. N.; Sharutin, V. V.; Molokova, O. V. Thermodynamic Properties of Tetraphenylantimony Benzophenoxymate in the Region of 0−450 K. Russ. J. Gen. Chem. 2009, 79, 717−723. (7) Letyanina, I. A.; Smirnova, N. N.; Markin, A. V.; Ruchenin, V. A.; Larina, V. N.; Sharutin, V. V.; Molokova, O. V. Thermodynamics of Tetraphenylantimony Acetophenoneoxymate. J. Therm. Anal. Calorim. 2011, 103, 355−363. (8) Markin, A. V.; Letyanina, I. A.; Smirnova, N. N.; Sharutin, V. V.; Molokova, O. V. Thermodynamic Characteristics of Triphenylantimony Bis(acetophenoneoximate). Russ. J. Phys. Chem. A 2011, 85, 1315−1321. (9) Markin, A. V.; Letyanina, I. A.; Smirnova, N. N.; Sharutin, V. V.; Molokova, O. V. Standard Thermochemical Characteristics of Formation of Triphenylantimony Bis(Acetophenoneoximate). J. Therm. Anal. Calorim. 2013, 111, 1499−1502. (10) Letyanina, I. A.; Markin, A. V.; Smirnova, N. N.; Gushchin, A. V.; Shashkin, D. V. Thermodynamic Characteristics of Triphenylantimony Diacrylate. Russ. J. Phys. Chem. A 2012, 86, 1189−1195. (11) Markin, A. V.; Letyanina, I. A.; Ruchenin, V. A.; Smirnova, N. N.; Gushchin, A. V.; Shashkin, D. V. Heat Capacity and Standard Thermodynamic Functions of Triphenylantimony Dimethacrylate over the Temperature Range from (0 to 400) K. J. Chem. Eng. Data 2011, 56, 3657−3662. (12) Letyanina, I. A.; Markin, A. V.; Smirnova, N. N.; Sologubov, S. S.; Sharutin, V. V. Heat Capacity and Standard Thermodynamic Functions of Triphenylantimony Bis(1-adamantanecarboxylate) over the Range from (0 to 520) K. J. Chem. Eng. Data 2013, 58, 3087− 3095. (13) Verkhovykh, V. A.; Kalistratova, O. S.; Grishina, A. I.; Artemova, V. G.; Gushchin, A. V. Synthesis of Triphenylbismuth Bis(2Methylpropenoate). Bulletin of SUSU Ser. Chem. 2015, 7, 61−65. (14) Wieser, M. E.; Holden, N.; Coplen, T. B.; Böhlke, J. K.; Berglund, M.; Brand, W. A.; De Bièvre, P.; Gröning, M.; Loss, R. D.; Meija, J.; et al. Atomic Weights of the Elements 2011 (IUPAC Technical Report). Pure Appl. Chem. 2013, 85, 1047−1078. (15) Gushchin, A. V.; Shashkin, D. V.; Prytkova, L. K.; Somov, N. V.; Baranov, E. V.; Shavyrin, A. S.; Rykalin, V. I. Synthesis and Structure of

26C(gr) + 12.5H 2(g) + 2O2 (g) + Bi(cr) → Ph3Bi(O2 CCMe = CH 2)2 (cr)

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where gr is graphite, cr is crystal, and g is gas.

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CONCLUSIONS The work reports the heat capacities of triphenylbismuth dimethacrylate Ph3Bi(O2CCMeCH2)2 that were measured between T = 5.3 and 330 K in the precision adiabatic vacuum calorimeter and within the range from T = 310 to 420 K with the differential scanning calorimetry. The reproducible anomaly was revealed from 150 to 170 K; intensive exothermic transition caused by the reductive decomposition with the polymerization of the sample under study was observed over the range from T = 385 to 420 K. The standard thermodynamic functions of crystalline Ph3Bi(O2CCMeCH2)2 were calculated over the range from T → 0 to 385 K. The standard entropy of Ph3Bi(O2CCMeCH2)2 (cr) at T = 298.15 K was calculated.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.5b01032. Experimental molar heat capacity of triphenylbismuth dimethacrylate Ph3Bi(O2CCMeCH2)2.(PDF)

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REFERENCES

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel: +7-831-462-3559. H



Article

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