Carbon–hydrogen vs. carbon–halogen oxidative addition of chlorobenzene to a cationic iridium(I) system — A density functional theory study

2009 ◽  
Vol 87 (10) ◽  
pp. 1460-1469 ◽  
Author(s):  
Hong Wu ◽  
Michael B. Hall
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Activation Barrier ◽  
Experimental Results ◽  
Density Functional Theory Study ◽  
Functional Theory ◽  
System A ◽  
Oxidative Additions ◽  
Calculated Activation ◽  
Calculated Activation Barrier

Density functional theory (DFT) is used to explore the competitive C−H and C−Cl oxidative additions (OA) of chlorobenzene to the cationic Ir(I) complex: [(PNP*)IrI]+ [PNP* = 2,6-bis((dimethylphosphino)methyl)pyridine]. Consistent with experimental results, the calculated activation barrier for C−H OA (ΔG‡ = 10.7 kcal mol–1) is lower than that for C−Cl OA (ΔG‡ = 19.7 kcal mol–1). However, the C−Cl OA product is calculated to be thermodynamically preferred as its ΔGo is 14.3 kcal mol–1 below that for the most stable C−H OA product.

A density functional theory study on the performance of graphene and N-doped graphene supported Au3 cluster catalyst for acetylene hydrochlorination

2016 ◽  
Vol 94 (10) ◽  
pp. 842-847 ◽  
Author(s):  
Fei Zhao ◽  
Yang Wang ◽  
Lihua Kang
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Energy Gap ◽  
Activation Barrier ◽  
Similar Reaction ◽  
Functional Theory ◽  
Acetylene Hydrochlorination ◽  
Doped Graphene ◽  
Calculated Activation ◽  
Calculated Activation Barrier

Density functional theory (DFT) calculation was used to investigate the mechanism of Au3 clusters, separately supported on pure graphene (Au3/graphene) and one graphitic N-doped graphene (Au3/N-graphene). These supported Au3 clusters were used to catalyze acetylene hydrochlorination. Results show that the graphene supporter could obviously enhance the adsorption of reactants. Also, N-atom doping could broaden the energy gap between the HOMO of graphene and the LUMO of Au3, leading to the significantly attenuated interaction between the Au3 cluster and graphene by more than 19 kcal/mol (1 cal = 4.184 J). The two catalysts possessed extremely similar reaction mechanisms with activation energy values of 23.26 and 23.89 kcal/mol, respectively. The calculated activation barrier declined in the order of Au3 < Au3/N-graphene < Au3/graphene, suggesting that Au3/N-graphene could be a potential catalyst for acetylene hydrochlorination.

Demystifying the mechanism of NMP ligands in promoting Cu-catalyzed acetylene hydrochlorination: insights from a density functional theory study

2020 ◽  
Vol 7 (17) ◽  
pp. 3204-3216
Author(s):  
Chaoyue Zhao ◽  
Xianming Zhang ◽  
Ziting He ◽  
Qingxin Guan ◽  
Wei Li
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Density Functional ◽  
Experimental Results ◽  
Density Functional Theory Study ◽  
Promoting Effect ◽  
Functional Theory ◽  
Acetylene Hydrochlorination ◽  
Inhibiting Effect ◽  
Catalytic Reactivity

Experimental results and DFT calculations revealed the promoting effect of NMP on catalytic reactivity and the inhibiting effect of NMP on the reduction of Cu2+ to Cu+ and Cu0, respectively.

MClx (M = Hg, Au, Ru; x = 2, 3) catalyzed hydrochlorination of acetylene — A density functional theory study

2013 ◽  
Vol 91 (2) ◽  
pp. 120-125 ◽  
Author(s):  
Mingyuan Zhu ◽  
Lihua Kang ◽  
Yan Su ◽  
Shanzheng Zhang ◽  
Bin Dai
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Chlorine Atom ◽  
Density Functional ◽  
Activation Barrier ◽  
Stable Complex ◽  
Atom Transfer ◽  
Density Functional Theory Study ◽  
Functional Theory ◽  
Complex Species

Density functional theory (DFT) calculations were used to study the mechanism for the hydrochlorination of acetylene catalyzed by MClx (M = Hg, Au, Ru; x = 2, 3). For the three catalysts, the reaction occurs via a one-shift chlorine atom transfer, which avoids the formation of highly stable complex species. The adsorbed HCl acts as a chlorine donor, while the C2H2 favors the chlorine abstraction. The calculated real activation barrier decreases in the order: HgCl2 > AuCl3 > RuCl3, which suggests that the RuCl3 would be a good candidate catalyst for the hydrochlorination of acetylene.

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