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Theoretical study of Ni+ assisted C-C and C-H bond activations of propionaldehyde in the gas phase.

ABSTRACT: The reactions of Ni+ with propionaldehyde in the gas phase have been systematically investigated using density functional theory at the B3LYP/def2-TZVP level. The decomposition reaction mechanism has been identified. Our calculations indicated that Ni+ can assist decomposition of propionaldehyde to form Ni+CO and C2H6 through two types of reaction channel: C-C bond activation and C-H bond activation. In addition, charge decomposition analysis (CDA) was carried out to obtain a deeper understanding for orbital interaction of the initial complex. The bonding properties of the species involved were discussed by means of diverse analysis methods including electron localization function (ELF) and atoms in molecules (AIM).

SUBMITTER: Zhao PP

PROVIDER: S-EPMC5521852 | biostudies-other | 2017 Aug

REPOSITORIES: biostudies-other

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Theoretical study of Ni+ assisted C-C and C-H bond activations of propionaldehyde in the gas phase.

Zhao Pei-Pei PP Wang Yong-Cheng YC Sheng Yang Y Jia Yi-Ming YM

Computational & theoretical chemistry 20170801

The reactions of Ni+ with propionaldehyde in the gas phase have been systematically investigated using density functional theory at the B3LYP/def2-TZVP level. The decomposition reaction mechanism has been identified. Our calculations indicated that Ni+ can assist decomposition of propionaldehyde to form Ni+CO and C2H6 through two types of reaction channel: C-C bond activation and C-H bond activation. In addition, charge decomposition analysi ...[more]

PMID: 28819583

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Project description:The potential energy surface (PES) of the C6H5 + NH2 reaction has been investigated by using ab initio CCSD(T)//B3LYP/6-311++G(3df,2p) calculations. The conventional transition-state theory (TST) and the variable reaction coordinate-TST (VRC-TST) have been used to predict the rate constants for the channels possessing tight and barrierless transition states, respectively. The Rice-Ramsperger-Kassel-Marcus/Master equation (RRKM/ME) theory has been utilized to determine the pressure-dependent rate constants for these reactions. The PES shows that the reaction begins with an exothermic barrierless addition of NH2 to C6H5 producing the vital intermediate state, namely, aniline (C6H5NH2, IS1). Once IS1 is generated, it can further isomerize to various intermediate states, which can give rise to different products, including PR4 (4,5,6-trihydro-1-amino phenyl + H2), PR5 (3,4,5,6-tetrahydro phenyl + NH3), PR6 (2,3,5,6-tetrahydro-1-imidogen phenyl + H2), PR9 (3,4,5,6-tetrahydro-1-imidogen phenyl + H2), and PR10 (2,5,6-trihydro-1-amino phenyl + H2), of which the most stable product, PR5, was formed by the most favorable channel going through the two advantageous transition states T1/11 (-28.9 kcal/mol) and T11P5 (-21.5 kcal/mol). The calculated rate constants for the low-energy channel, 1.37 × 10-9 and 2.16 × 10-11 cm3 molecule-1 s-1 at T = 300, P = 1 Torr and T = 2000 K, P = 760 Torr, respectively, show that the title reaction is almost pressure- and temperature-dependent. The negative temperature-dependent rate coefficients can be expressed in the modified Arrhenius form of k 1 = 8.54 × 1013 T -7.20 exp (-7.07 kcal·mol-1/RT) and k 2 = 2.42 × 1015 T -7.61 exp (-7.75 kcal·mol-1/RT) at 1 and 10 Torr, respectively, and in the temperature range of 300-2000 K. The forward and reverse rate coefficients as well as the high-pressure equilibrium constants of the C6H5 + NH2 ↔ IS1 process were also predicted; their values revealed that its kinetics do not depend on pressure at low temperature but strongly depend on pressure at high temperature. Moreover, the predicted formation enthalpies of reactants and the enthalpy changes of some channels are in good agreement with the experimental results.

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Theoretical study of Ni+ assisted C-C and C-H bond activations of propionaldehyde in the gas phase.

Publications

Theoretical study of Ni<sup>+</sup> assisted C-C and C-H bond activations of propionaldehyde in the gas phase.

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