Theoretical Studies on the Reaction Mechanism of Criegee Intermediates RCHOO(R=H, CH3) with NCO Radical†

doi:10.7503/cjcu20160803

Abstract

Abstract:

A comprehensive theoretical study about the reaction of RCHOO(R=H, CH₃) with NCO was performed at the CCSD(T)/aug-cc-pVTZ//B3LYP/6-311+G(2df,2p) level. The rate coefficients for the dominant reaction channels were determined at 298—500 K via conventional transition state theory(TST) with a Eckart tunneling. The results show that the detailed mechanism mainly includes addition, oxidation and hydrogen abstraction reactions. N and O atoms of the NCO radical can react to RCHOO(R=H and CH₃) in each reaction mode. Moreover, the end O atom of NCO addition to RCHOO(R=H and CH₃) α-C is favored for the addition reaction, while the reactions involving the end N atom of NCO is advantaged in both oxidation and hydrogen abstraction. The methyl substituents in the CH₂OO produce an increase of the reactivity. Anti-CH₃CHOO shows a higher reactivity than syn-CH₃CHOO towards addition and oxidation reaction, but for the hydrogen abstraction, syn-CH₃CHOO is significantly more reactive than anti-CH₃CHOO. The contribution of anti-CH₃CHOO to the overall rate constant is greater than that of syn-CH₃CHOO, and the total rate constant satisfies a strong negative temperature effect.

Key words: Criegee intermediate, NCO, Reaction mechanism, Rate constant

CLC Number:

0643.1

TrendMD:

MA Qian, WANG Weina, ZHAO Qiangli, LIU Fengyi, WANG Wenliang. Theoretical Studies on the Reaction Mechanism of Criegee Intermediates RCHOO(R=H, CH₃) with NCO Radical^†[J]. Chem. J. Chinese Universities, 2017, 38(4): 613.

Figures/Tables 9

Scheme 1 Ozonolysis of alkenes forming carbonyl compound and RCHOO(R=H, CH3)

Fig.1 Optimized geometries of reactants and products in the reaction of RCHOO(R=H,CH3)+NCO at the B3LYP/6-311+G(2df,2p) levela. At the B3LYP/AVTZ level[26]; b. at the CCSD(T)-F12/AVTZ level[27]; c. at the CCSD(T)/aug-co-pCV5Z level[28]; d. experimental values from ref.[29]; e. at the BH&HLYP/6-311++G(3df, 3pd) level[30]; f. at the NEVPTZ(1,1)/aug-cc-pVDZ[31]. The charges of the carbon, nitrogen and oxygen atom obtained from NBO analysis, bond lengths are in nm, bond angles are in degrees.

Table 1 Formation enthalpies ΔfH 0— for some species at the G4 level

Species	Δ_fH^0—/(kJ·mol^-1)	Species	Δ_fH^0—/(kJ·mol^-1)
NCO	144.18	CH₂(OO)NCO	-57.87
HNCO	-108.06(-110.00)^[32]	IM1	66.08
HCHO	-112.11(-108.70)^[32]	IM2	-98.47
CH₃CHO	-166.57(-170.70)^[32]	IM3	14.95
CH₂OO	102.26(104.92)^[33]	IM4	10.67
RC1	202.33	CH₃CH(OO)NCO	-99.11
RC2	129.48	HOCN	-10.46
RC3	169.67	syn-CH₃CHOO	37.78
RC4	152.52	anti-CH₃CHOO	52.69

Scheme 2 Possible reaction channels of RCHOO(R=H, CH3) with NCOTSna-N/O, TSno-N/O and TSnh-N/O(n=1—5) stand for transition states of the reaction of addition, oxidation and hydrogen abstraction, respecitively.

Fig.2 SOMO orbital pictures and orbital energy(9.35 eV) of NCO

Fig.3 Potential energy surface of the addition reaction at the CCSD(T)//B3LYP/6-311+G(2df,2p) level

Fig.4 Potential energy surface of the oxidation at the CCSD(T)/aug-cc-pVTZ//B3LYP/6-311+G(2df,2p) level

Fig.5 Potential energy surface of the favorable hydrogen abstraction channels at the the CCSD(T)/aug-cc-pVTZ// B3LYP/6-311+G(2df,2p) level

Fig.6 Fitted plots of the rate constants versus the reciprocal of temperature for the favorable channels over the range of 298—500 KO attacking Cl: a. R2; b. R7; c. R13; N attacking O1: d. R3; e. R8; f. R14; N attacking H: g. R5; h. R10; i. R16.

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Theoretical Studies on the Reaction Mechanism of Criegee Intermediates RCHOO(R=H, CH₃) with NCO Radical^†

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