Supplementarymaterial
S1.
Fig. 13. The experimental setup for the experiments on he alkynes oxidative carbonylation
in an open system.
The researcher from the Newcastle University (UK) carried out experiments on the phenylacetylene carbonylation in a large-volume reactor (450 ml) HEL SIMULARTM in a flow system [21]. The reactor was a one-liter glass vessel fitted with a jacket (Fig.19). Stirring was carried out with a mechanical stirrer; the system of the high-precision temperature control includeddevice an external cooling system and an electric heater placed inside the reactor. The reactor was equipped with a gas speed controller, a temperature sensor (Pt 100) and a pH electrode. The pressure of the gas mixture was atmospheric. All reagents were purchased from Sigma Aldrich and used without further purification. In experiments, air was used instead of oxygen. The results of oscillatory experiments were published in [21-24]
Fig. 14. Experimental setup for carrying out experiments on the oxidative carbonylation
of alkynes in an open system.
S2.The composition of the initial and reaction mixture of gases was analyzed by gas-adsorption chromatography with a 3-m packed columns (3 mm in diameter) filled with activated carbon AG-3 (air, CO, CO2, separation temperature-1600C) and molecular sieves 13 X (O2, N2, CO, separation temperature - 400C). In both cases, 0.25–0.5-mm fractionwas used,thermal conductivity detector, and argon as a carrier gas.
Concentrations in the contact solution of phenylacetylene and carbonylation products were analized by the method of GLC with a 3-m packing columns(3 mm in diameter), filled with "Poropak-P" and 10% “Apiezon-L” on inertone, respectively, fraction 0.25 - 0.3 mm. The separation conditions were the same: thermal conductivity detector, the carrier gas was helium, and the separation temperature - 230° C.
The process was carried out at atmospheric pressure of CO-O2mixture (3: 2 by volume). Part of the carbon monoxide during the reaction is oxidized to CO2. The products obtained in the oxidative carbonylation of phenylacetylene were identified by the chromato-mass spectrometry. Products of the reactions were analyzed by GC “Agilent Technology” (USA), supplied by mass - detector (capillary column HS-50; diameter of a column - 0, 32 mm; thickness of a phase layer - 0,32 microns; a phase – polymethylsiloxan with a layer thickness of 0.52 μm).The temperature of the evaporator was 1500C, the column temperature was programmed: for 5 minutes it was maintained at T = 500C, then for 12 minutes the temperature was raised at a speed of 150C/min to T = 2300C, then this temperature was maintained for 5 more minutes.
S3.
(a)
[KI]0 = 0.2M [KI]0 = 0.4M
(b)
[PdI2]0= 0.005M[PdI2]0 = 0.01M
(c)
[O2]0= 6 V%[O2]0= 15 V%
Fig. 15. Effect of initial concentrations of KI, PdI2 and the partial pressures
of CO and O2 on the oscillations characteristics in the process of PhA oxidative carbonylation
S4.
Fig. 16. Experiment on the PhA oxidative carbonylation.
([KI]0 = 0.4 М; [PdI2]0 = 0.00022M; [PhА]0 = 0.1 M)
S5. Table 1. Influence of solvents and iodides on the oscillations mode in the system
PdI2 - MI - PhC≡CH - ROH * [25].
Methanol / KI / –90 +150 / 2,0 4,6 / yes
Methanol / CsI / –50 +210 / 0,8 5,0 / yes
Propan-2-ol / KI / –65 –80 / 3,5 4,3 / no
Propan-2-ol / LiI / –10 +10 / 2,4 2,7 / no
Ethanol / KI / –100 –120 / 3,4 3,6 / no
n-Butanol / KI / –20 – 40 / 3,64,1 / + CH3ONa
n-Butanol / LiI / –110 –160 / 1,6 2,7 / no
n-Butanol / NH4I / +20 +40 / 2,6 3,2 / no
n-Butanol / RbI / –40 –60 / 2,42,6 / + CH3ONa
*) MI is the iodide used in the experiment; RON is a solvent.
From the data of Table 1 it can be seen that most of iodide - alcohol combinations are characterized by a lower pH than in standard experiment and the lack of oscillations. The nature of the cation (Rb+, Cs+, NH4+, K+) added with the iodide ion generally has a smallinfluence on the oxidative carbonylation of phenylacetylene in the oscillation regime.
S6.
Fig. 8. PhA Oxidative carbonylation in the LiBr-PdBr2-H2O-acetone system.
Oscillations of pH values and consumed gases volumes.
(LiBr=0.2М; PdBr2=0.01М; PhА=0,1М; V(CH3)2СO=10ml;
[CO]0 : [O2]0 = 1:2,9; Н2О=137 μl (0.77 M))
S7. The preliminary mechanism for oxidative PhA carbonylation to phenylmaleic anhydride (3):
(3)
This mechanism can be presented in a generalized form as follows (4):
(4)
This mechanism is based on the hypothesis of the activity of Pd (I) compounds. There are stages in it that are nonlinear, and this is a necessary condition for the realization of the oscillatory regime. Moreover, you can seein the generalized scheme, there are the interactionof the reaction intermediatesby the type of negative feedbackin the proposed mechanism. Therefore, we believe that this mechanism could serve very well as a starting point for modeling of the oscillations in this system.
S8.
Fig. 17. The general oscillations pattern of pH and reaction heat (Q) in experiments
carried out in a flow reactor.
([KI]0 = 0.5 М; [PdI2]0 = 0.0124M; [PhА]0 = 0.126 M; V CH3OH= 450 ml;
flow rate of gases: CO = 50ml/min; air = 50ml/min)
Fig. 18. Change of pH and heat of reaction (Q) in oscillatory mode in the flow system.
([KI]0 = 0.5 М; [PdI2]0 = 0.0124M; [PhА]0 = 0.126 M; V CH3OH= 450 ml;
flow rate of gases: CO = 50ml/min; air = 50ml/min) (A fragment of Fig. 17)
S9.
(a)
(b)
Fig. 19. Oxidative carbonylation of FA with different catalysts
(a) CsPd4I5·12H2O; (b) KPd4I5;
([KI]0 = 0.4 M; [Pd+I]0 = 0.02 M; [PhА]0 = 0.1 M; [CO]0 : [O2]0 = 3:2)
S10.
(a) (b)
Fig. 20. The comparison of modeling results (a) and experimental data (b)
of phenylacetylene oxidative carbonylation.
([KI]0=0.4M; [PhА]0= 0.1M; [CO]0 : [O2]0= 3:2; [PdI2]0= 0.005M)
S11.
Fig. 21. Changes of reagent concentrations over time,
calculated by model of the mechanism (5 - 11).