欢迎您！东篱公司
退出
-
申报数据库
-
立项数据库
-
成果数据库
-
项目获奖数据库
中文摘要：
铁及其复合物催化的C—X键功能化日益引起人们的重视.采用密度泛函理论（DFT）,在B3LYP/def2-SVP水平下详细研究了Fe＋与CH3X（X=Cl,Br,I）的反应活性和机理.计算结果表明标题反应存在两种反应机制,即插入机制和SN2机制.从机理上来看,在插入机理中,反应都始于Fe＋离子从侧面进攻CH3X,生成产物FeX＋和CH3;而在SN2机制中,反应则始于Fe＋离子从背后进攻CH3X,生成产物3FeCH＋和X.从我们的计算可以看出,四重态或六重态下的Fe＋离子在C—X键活化中展现了截然不同的催化活性;在所有通道中,都以四重态为主导;SN2机制中相对较高的决速能垒使其丧失了竞争性.再者,计算表明在所有的插入机制中,所有通道都是放热的,而在SN2机制中,仅有X=I时,反应是放热的.此外,计算表明这些反应属于两态反应活性,两种机制中,在反应的入口和出口存在最小能量交叉点.此外,反应途径电子结构追踪分析表明自旋极化对能量影响较大,调控着反应采取的反应通道和主副产物比例.通过本文的理论研究,尤其是详细的电子结构分析,为铁催化剂活化C—X键和C—C耦联反应提供了线索和以铁为基的催化剂设计提供理论依据.
英文摘要：
The C--X bond functionalization catalyzed by iron and their complexes has attracted much attention. Using den- sity functional theory （DFT）, we herein studied the reactivity and mechanism of iron cation （Fe＋） towards C--X bond cleav- age of CH3X （X：C1, Br, I） at B3LYP/def2-SVP level of theory. The results show that there are two possible pathways available for the title reactions, i.e. the insertion mechanism and the SN2 mechanism, respectively. Mechanistically, in the insertion mechanism, the reactions stem from Fe＋ attacking on the side of CH3X and results in the generation the products FeX＋ and CH3＂; whereas in the SN2 mechanism, the Fe＋ initially attacks the substrate from the back of C--X yielding FeCH3＋and X＇. The results show that the sextet and the quartet states ofFe~ demonstrate quite distinct reactivity towards the cleavage of C--X bonds in the most potential pathways, and the quartet pathways are dominant in all the pathways. The rela- tive higher barriers in the SN2 pathways results in their lower competitiveness in the title reactions. In addition, our results show that, for all the three reaction systems, the insertion mechanism is exothermic; whereas for the SN2 mechanism, only X =I is exothermic, however. Furthermore, the calculations also show that these reactions demonstrate two-state reactivity （TSR） scenario. There are minimum energy crossing points （MECPs） between the sextet and quartet state on potential energy surfaces （PESs） both at the entrance and export sides for the two reaction mechanisms. On the other hand, the electron trans- fer evolution analysis indicates that the spin polarization plays important role in the stabilization of the potential energy sur- faces and as a result, it controls the pathways by which it takes place and the branch ratio of the major products and byprod- ucts. This thorough theoretical study, especially the detailed electronic structure analysis, may provide important clues for understanding the C--X bond activation a
同期刊论文项目
同项目期刊论文
Theoretical study of the imidazolidinone catalyzed 1,4-addition of N,N-dimethyl-3-anisidine with alp
Mechanism for the formation of benzene in the Titan's atmosphere: A theoretical study on the mechani
Evaporation- and surface-induced morphology of symmetric diblock copolymer thin films: a multibody d
Ab Initio Investigation on a New Class of Binuclear Superalkali Cations M2Li2k+1+ (F2Li3+, O2Li5+, N
POSITIONING OF Ftz-F1 DOMAIN AFFECTS ON THE ACTIVITY OF HUMAN LRH-1: MOLECULAR DYNAMICS STUDY ON HUM
Lithium Salt of NH2-substituted Graphene Nanoribbon with Twofold Donor-acceptor Framework: Large Non
Exceptionally Large Second-Order Nonlinear Optical Response in Donor-Graphene Nanoribbon-Acceptor Sy
Comparative Insight into Electronic Properties and Reactivities toward C-H Bond Activation by Iron(I
The effect of the axial ligand on distinct reaction tunneling for methane hydroxylation by nonheme i
Alkali Metal Atom-Aromatic Ring: A Novel Interaction Mode Realizes Large First Hyperpolarizabilities
Successive hydrogenation starting from the edge(s): an effective approach to fine-tune the electroni
Analysis of an alternative to the H-atom abstraction mechanism in methane C-H bond activation by non
Comparison of the FeO2+ and FeS2+ Complexes in the Cyanide and Isocyanide Ligand Environment for Met
Mechanism Insights of Ethane C-H Bond Activations by Bare [Fe-III=O](+): Explicit Electronic Structu
Mechanism of benzene hydroxylation by high-valent bare Fe(IV)=O(2+): explicit electronic structure a
Comparison of the Active-Site Design of Molybdenum Oxo-Transfer Enzymes by Quantum Mechanical Calcul
Mechanism of benzene hydroxylation by high-valent bare Fe-IV=O2+: explicit electronic structure anal
Direct ab initio dynamics study of rate constants and kinetic isotope effects for C-2(A(3)Pi(u)) + C
Theoretical investigation on structures, stability and properties of [P, X, Y] (X=C, Si; Y?=?O, S) i
Molecular simulations study of ligand-release mechanism in an odorant-binding protein from the south
Investigation on Nonlinear Optical Properties of Foreign-atom Doping Boron Nitride Nanotube with Vac
(Super)alkali atoms interacting with the sigma electron cloud: a novel interaction mode triggers lar
DFT Study on Mechanism of N-Alkylation of Amino Derivatives with Primary Alcohols Catalyzed by Coppe
Molecular Dynamics Simulation Study on the Effect of Mutant(Met108-Leu108) on Interactions Between A
Origins of Selective C(sp(2))-H Activation Using Transition Metal Complexes with N,N-Bidentate Direc
Evaporation-induced Morphology Pattern of Triblock Copolymer A(5)B(10)C(5) in Thin Film: a Multibody
Introducing the Triangular Defect to Effectively Engineer the Wide Band Gap of Boron Nitride Nanorib
Theoretical Study on Mechanism of Cinchona Alkaloids Catalyzed Asymmetric Conjugate Addition of Dime
Multifunctional Polymer Mach-Zehnder Optical Switch/Filter Using Side-Coupled M X N Electrooptic Mic
A computational mechanistic study of pH-dependent alcohol dehydrogenation catalyzed by a novel [C,N]
Molecular simulations study of novel 1,4-dihydropyridines derivatives with a high selectivity for Ca
Hydrogen generation from alcohols (α-hydroxy carboxylic acids) and alcohol–ammonia coupling in aqueo
A First-PrinciplesInvestigation on the Effect of the Divacancy Defect on the Band Structures ofBoron
Theoretical investigation on the interaction of subnano platinum clusters with graphene using DFT me
Molecular chargetransfer via π–π interaction: an e？ectiveapproach to realize the half-metallicity an
期刊信息
位置：