A combined density functional theory and molecular mechanics (QM/MM) study of single site ethylene polymerization catalyzed by [Cp{NC(t-Bu)2}TiR+] in the presence of the counterion (CH3B(C6F5)3–)1

2003 ◽  
Vol 81 (11) ◽  
pp. 1413-1429 ◽  
Author(s):  
Kumar Vanka ◽  
Zhitao Xu ◽  
Tom Ziegler
Keyword(s):  
Density Functional Theory ◽  
Ethylene Polymerization ◽  
Density Functional ◽  
Hydrogen Transfer ◽  
Single Point ◽  
Metal Centre ◽  
Functional Theory ◽  
Tertiary Butyl ◽  
Initiation Step ◽  
Cis And Trans

Calculations have been carried out to investigate the insertion of the ethylene monomer into the Ti–alkyl bond for the systems CpNC(t-Bu)2RTi-µ-Me-B(C6F5)3 (R = Me and Pr), using density functional theory. A validated QM/MM model was used to represent the counterion. The tertiary butyl groups in the ligands were modeled with QM/MM, with hydrogens being used as the capping atoms. Solvent effects were incorporated with single point solvent calculations done with cyclohexane (ε= 2.023) as the solvent. With R = Me (the initiation step), approach of the ethylene cis and trans to the -µ-Me bridge was considered. Insertion was found to be endothermic, with ΔHtot being 12.7 kcal/mol (cis) and 15.5 kcal/mol (trans). The propagation step was then studied for the contact ion pair CpNC(t-Bu)2PrTi-µ-Me-B(C6F5)3 (4). Different conformations of the propyl chain in 4 were considered by altering θ, the dihedral angle formed between the Cβ-Cα-Ti and the Cα-Ti-µC planes. The resting states were found to be at θ = –69° (4a), 177° (4b), and 53° (4c). A maxima was found near θ = 0° (4d). The cis and trans approaches of the ethylene monomer were considered for each of the four cases. The cis approach towards 4a and trans approach towards 4d led to insertion, with displacement of the counterion from the metal centre. The insertion barriers were found to be 17.8 kcal/mol, for the cis approach towards 4b and 16.4 kcal/mol for the trans approach towards 4d. The cis approaches towards conformers 4a and 4c showed common characteristics, with uptake barriers being higher than the subsequent insertion barriers in the two cases. Uptake barriers were 13.6 kcal/mol {TS(4a–7a)} and 10.7 kcal/mol {TS(4c–8a)}. The corresponding insertion barriers were 11.8 kcal/mol {TS(7a–13a)} and 8.4 kcal/mol {TS(8a–13a)}. The trans approaches towards conformers 4a and 4c led to insertion barriers of about 15.1 kcal/mol (lower than for the 4b and 4d cases). The cis approach towards 4d and trans approach towards 4b were found to lead to hydrogen transfer from the propyl chain to monomer, terminating the chain. Termination barriers were high — greater than 19.0 kcal/mol. This suggested that ethylene insertion would be favoured over termination during the propagation step.Key words: homogeneous catalysis, counterion, initiation, propagation, termination.

Binuclear O2 activation and hydrogen transfer mechanism for aerobic oxidation of alcohols

2020 ◽  
Vol 10 (7) ◽  
pp. 2183-2192
Author(s):  
Zhiyun Hu ◽  
Hongyu Ge ◽  
Xinzheng Yang
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Hydrogen Transfer ◽  
Aerobic Oxidation ◽  
Density Functional Theory Calculations ◽  
Transfer Mechanism ◽  
Functional Theory ◽  
O2 Activation ◽  
Oxidation Of Alcohols

Density functional theory calculations reveal a binuclear O2 activation and hydrogen transfer mechanism with spin-crossovers for aerobic oxidation of alcohols.

THEORETICAL STUDIES ON THE REACTION MECHANISM OF HNCS WITH CH2CH RADICAL

2007 ◽  
Vol 06 (01) ◽  
pp. 1-12 ◽  
Author(s):  
JIAN-HUA XU ◽  
LAI-CAI LI ◽  
YAN ZHENG ◽  
JUN-LING LIU ◽  
XIN WANG
Keyword(s):  
Density Functional Theory ◽  
Reaction Mechanism ◽  
Reaction Mechanisms ◽  
Density Functional ◽  
Hydrogen Transfer ◽  
Main Product ◽  
Reaction Pathways ◽  
Theoretical Studies ◽  
Functional Theory ◽  
Ch Radical

The reaction mechanisms of HNCS with CH 2 CH radical have been investigated by density functional theory (DFT). The geometries and harmonic frequencies of the reactants, intermediates, transition states and products have been calculated at the B3LYP/6-311++G(d,p) level. The results show that the reaction is very complicated. Nine possible reaction pathways were identified. The results show that the most feasible reaction channel is the hydrogen-transfer pathway CH 2 CH + HNCS → IMA1 → TSA1 → CH 2 CHH + NCS . The pathway VIC C-S addition channel ( CH 2 CH + HNCS → TSD5 → IMD4 → TSD9 → CH 2 CHS + CNH ) can also occur easily. Ethene and radical NCS is the main product of the studied reaction, and product P8 ( CH 2 CHS and CNH ) may also be observed. Compared with our previous study on the reaction HNCS + CH 2 CH , the present reaction is easier to proceed.

scholarly journals Simulation Study of Structural and Electronic Properties for Adducts complexes of Bis(Acetylacetonato)oxoVandium (IV) with 4-(Para-substituted phenyl)-1,2,3-Selenadiazole

2021 ◽  
Vol 2063 (1) ◽  
pp. 012002
Author(s):  
Dalal H Alsawad ◽  
Ali A Al-Riyahee ◽  
Ali J Hameed
Keyword(s):  
Density Functional Theory ◽  
Electronic Properties ◽  
Molecular Orbital ◽  
Density Functional ◽  
Functional Theory ◽  
Structural And Electronic Properties ◽  
Lowest Unoccupied Molecular Orbital ◽  
Reorganization Energies ◽  
Cis And Trans ◽  
Optimized Geometries

Abstract A series of 4-(para-substituted phenyl)-1,2,3-selenadiazole adducts of [VO(acac)2] were studied by density functional theory (DFT) calculations. The 4-(para-substituted phenyl)-1,2,3-selenadiazole molecules have been selected to be bound with vanadium atom in [VO(acac)2] through Se, N2 and N3. The resulting adducts have been investigated in two geometries (cis and trans) in order to show the effect of such structural change on the electronic properties of the studied adducts. The optimized geometries, (binding and reorganization) energies and the spatial distribution of the highest molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the adducts are presented and discussed.

Mechanisms of rearrangements in platinacyclobutane chemistry

2020 ◽  
pp. 1-8
Author(s):  
Richard J. Puddephatt
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Hydrogen Transfer ◽  
Activation Energies ◽  
High Activation ◽  
Functional Theory ◽  
Hydride Complexes ◽  
Decomposition Reactions ◽  
Trigonal Bipyramidal ◽  
Mechanisms Of Formation

The mechanisms of formation, decomposition, and isomerisation of platinacyclobutane complexes [PtCl2(C3H6)L2] (L is typically pyridine) are discussed on the basis of density functional theory (DFT). The isomerisation and decomposition reactions occur through 5-coordinate intermediates [PtCl2(C3H6)L] that cannot be directly detected. These 5-coordinate complexes are predicted to have distorted square pyramidal structures, but a pinched trigonal bipyramidal (PTBP) stereochemistry is easily accessible. Both α- and β-elimination from these complexes to give hydride complexes [PtHCl2(C3H5)L] are predicted to have high activation energies. The isomerisation of [PtCl2(C3H6)L2] to the ylide complex [PtCl2{CH(L)CH2CH3)L] is instead predicted to occur after cleavage of a Pt–C bond to give an intermediate that can be considered as a corner platinated cyclopropane, leading to 1,3-hydrogen transfer without a hydridoplatinum intermediate. The reaction of [PtCl2{CH(L)CH2CH3}L] to give the alkene complex [PtCl2(CH2 = CHCH3)L] involves dissociation of the C–L bond followed by a 2,1-hydrogen transfer. The selectivity of related reactions from phenylcyclopropane follows naturally from these mechanisms.

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