Reaction paths and transition states of the C-C and C-H bond cleavage in the aromatic anthracene and phenanthrene molecules

Abstract

The reaction paths of the C-C and C-H bond cleavage in the anthracene and phenanthrene aromatic molecules are studied by applying the ab-initio DFT method. It is found that the C-C bond cleavage proceeds via a singlet aromatic transition state, compelled through a disrotatoric ring opening reaction. A suprafacial H atom shift follows the transition state, leading to the formation of a methylene -CH2 and an acetylenic or allenic moiety

C-C and C-H bond cleavage reactions in the chrysene and perylene aromatic molecules: An ab-initio density functional theory study

“…The ab-initio DFT study for the C-H bond cleavage reaction of both molecules, similar to those of the formerly calculated molecules [1][2][3][4][5][6][7], shows common features, for both chrysene and perylene which might be concluded in the following statements; (i) All these reactions pass through planar S, TS's, (ii) They show common reaction energy, for the S and T products, of ~116-117 kcal/mol (iii) They show different values for the activation energy, Tables 1 and 2.…”

“…In former reports, we described the application of the abinitio DFT, quantum mechanical method, for the estimation of the structures and energies of the transition states (TS) and reaction products (RP) of the C-C and C-H bond cleavage reactions for a series of polyaromatic hydrocarbon (PAH) molecules [1][2][3][4][5][6][7]. The following properties of the C-C bond cleavage reactions could be concluded;…”

C-C and C-H bond cleavage reactions in the chrysene and perylene aromatic molecules: An ab-initio density functional theory study

“…The ab-initio DFT study for the C-H bond cleavage reaction of both molecules, similar to those of the formerly calculated molecules [1][2][3][4][5][6][7], shows common features, for both chrysene and perylene which might be concluded in the following statements; (i) All these reactions pass through planar S, TS's, (ii) They show common reaction energy, for the S and T products, of ~116-117 kcal/mol (iii) They show different values for the activation energy, Tables 1 and 2.…”

“…In former reports, we described the application of the abinitio DFT, quantum mechanical method, for the estimation of the structures and energies of the transition states (TS) and reaction products (RP) of the C-C and C-H bond cleavage reactions for a series of polyaromatic hydrocarbon (PAH) molecules [1][2][3][4][5][6][7]. The following properties of the C-C bond cleavage reactions could be concluded;…”

C-C and C-H bond cleavage reactions in acenaphthylene aromatic molecule, an ab-initio density functional theory study

“…Due to their industrial importance, the study of the thermal degradations of polycyclic aromatic hydrocarbons (PAH) had been a subject for numerous experimental and theoretical investigations [1][2][3][4][5][6][7][8][9][10][11][12][13]. In previous papers, we reported quantum mechanically calculated structures and energies of the transition states (TS) and reaction products (RP) of the C-C and C-H bond cleavage reactions for a number of poly-aromatic hydrocarbon molecules [14][15][16][17][18][19][20][21]. We applied for these treatments the ab-initio Density Functional Theory (DFT) method [23][24][25][26][27].…”

Understanding the Thermal Cracking for Anthracene Molecule : A DFT Approach

“…Aromatic compounds are present in high concentrations in crude oil and composited about 3-4% of the heavy crude oil [2]. The term cracking applies to the decomposition of petroleum where by the higher molecular weight constituents of petroleum are converted to low molecular weight products [3].…”

C-C and C-H bond cleavage reactions in the chrysene and perylene aromatic molecules: An ab-initio density functional theory study

“…The ab-initio DFT study for the C-H bond cleavage reaction of both molecules, similar to those of the formerly calculated molecules [1][2][3][4][5][6][7], shows common features, for both chrysene and perylene which might be concluded in the following statements; (i) All these reactions pass through planar S, TS's, (ii) They show common reaction energy, for the S and T products, of ~116-117 kcal/mol (iii) They show different values for the activation energy, Tables 1 and 2.…”

“…In former reports, we described the application of the abinitio DFT, quantum mechanical method, for the estimation of the structures and energies of the transition states (TS) and reaction products (RP) of the C-C and C-H bond cleavage reactions for a series of polyaromatic hydrocarbon (PAH) molecules [1][2][3][4][5][6][7]. The following properties of the C-C bond cleavage reactions could be concluded;…”

C-C and C-H bond cleavage reactions in acenaphthylene aromatic molecule, an ab-initio density functional theory study

“…Due to their industrial importance, the study of the thermal degradations of polycyclic aromatic hydrocarbons (PAH) had been a subject for numerous experimental and theoretical investigations [1][2][3][4][5][6][7][8][9][10][11][12][13]. In previous papers, we reported quantum mechanically calculated structures and energies of the transition states (TS) and reaction products (RP) of the C-C and C-H bond cleavage reactions for a number of poly-aromatic hydrocarbon molecules [14][15][16][17][18][19][20][21]. We applied for these treatments the ab-initio Density Functional Theory (DFT) method [23][24][25][26][27].…”

Understanding the Thermal Cracking for Anthracene Molecule : A DFT Approach

“…Aromatic compounds are present in high concentrations in crude oil and composited about 3-4% of the heavy crude oil [2]. The term cracking applies to the decomposition of petroleum where by the higher molecular weight constituents of petroleum are converted to low molecular weight products [3].…”

C-C and C-H bond cleavage reactions in the chrysene and perylene aromatic molecules: An ab-initio density functional theory study

“…The ab-initio DFT study for the C-H bond cleavage reaction of both molecules, similar to those of the formerly calculated molecules [1][2][3][4][5][6][7], shows common features, for both chrysene and perylene which might be concluded in the following statements; (i) All these reactions pass through planar S, TS's, (ii) They show common reaction energy, for the S and T products, of ~116-117 kcal/mol (iii) They show different values for the activation energy, Tables 1 and 2.…”

“…In former reports, we described the application of the abinitio DFT, quantum mechanical method, for the estimation of the structures and energies of the transition states (TS) and reaction products (RP) of the C-C and C-H bond cleavage reactions for a series of polyaromatic hydrocarbon (PAH) molecules [1][2][3][4][5][6][7]. The following properties of the C-C bond cleavage reactions could be concluded;…”

C-C and C-H bond cleavage reactions in acenaphthylene aromatic molecule, an ab-initio density functional theory study

“…Due to their industrial importance, the study of the thermal degradations of polycyclic aromatic hydrocarbons (PAH) had been a subject for numerous experimental and theoretical investigations [1][2][3][4][5][6][7][8][9][10][11][12][13]. In previous papers, we reported quantum mechanically calculated structures and energies of the transition states (TS) and reaction products (RP) of the C-C and C-H bond cleavage reactions for a number of poly-aromatic hydrocarbon molecules [14][15][16][17][18][19][20][21]. We applied for these treatments the ab-initio Density Functional Theory (DFT) method [23][24][25][26][27].…”

Understanding the Thermal Cracking for Anthracene Molecule : A DFT Approach

“…Aromatic compounds are present in high concentrations in crude oil and composited about 3-4% of the heavy crude oil [2]. The term cracking applies to the decomposition of petroleum where by the higher molecular weight constituents of petroleum are converted to low molecular weight products [3].…”