Effects of Axial Solvent Coordination to Dirhodium Complexes on Reactivity and Selectivity in C–H Insertion Reactions: A Computational Study

Diazo Compounds ◽

Insertion Reactions ◽

Functional Theory ◽

Axial Ligation ◽

Donor Acceptor ◽

Solvent Molecules ◽

Dirhodium Complexes

Density functional theory calculations were used to systematically explore the effects of axial ligation by solvent molecules on the reactivity and selectivity of dirhodium tetracarboxylates with diazo compounds in the context of C–H insertion into propane. Insertions on three types of diazo compounds—acceptor/acceptor, donor/acceptor, and donor/donor—promoted by dirhodium tetraformate were tested with and without axial solvent ligation for no surrounding solvent, dichloromethane, isopropanol, and acetonitrile. Magnitudes, origins, and consequences of structural and electronic changes arising from axial ligation were characterized. The results suggest that axial ligation affects barriers for N2 extrusion and C–H insertion, the former to a larger extent.

Wechselwirkungen in Molekülkristallen, 166 [1, 2]. Polyiod-Moleküle I2C=CI2, (IC)4S, (IC)4NH, (IC)4N-CH3 und HCI3: Strukturbestimmung nach Kristallzüchtung oder durch Dichtefunktionaltheorie-Berechnung / Interaction in Molecular Crystals, 166 [1, 2], Polyiodo Molecules I2C=CI2, (IC)4S, (IC)4 NH, (IC)4N-CH and HCI3: Structure Determination Following Crystallization or by Density Functional Theory Calculation

Zeitschrift für Naturforschung B ◽

10.1515/znb-2001-0104 ◽

2001 ◽

Vol 56 (1) ◽

pp. 13-24 ◽

Cited By ~ 4

Author(s):

Hans Bock ◽

Sven Holl ◽

Volker Krenzel

Keyword(s):

Density Functional ◽

Crystal Packing ◽

Density Functional Theory Calculation ◽

Density Functional Theory Optimization

Structural Data ◽

Basis Sets ◽

Functional Theory ◽

Donor Acceptor ◽

Abstract The structures of tri-and tetraiodo-substituted carbon compounds are determined either experimentally by X-Ray Structure Analysis or, because crystallization of tetraiodothiophene could not be achieved, approximated by Density Functional Theory optimization of structural data from a donor/acceptor complex. The structures show noteworthy details such as a second polymorph of tetraiodoethene crystallized by sublimation or herringbone crystal packing patterns of tetraiodopyrrole derivatives. All molecular geometries are discussed and compared based on relativistic density functional theory calculations with 6 -31G* basis sets including iodine pseudopotentials. They reproduce even finer structural details due to van der Waals repulsion of the bulky iodo substituents. Natural Bond Orbital (NBO) charge distributions suggest positive partial charges at all iodine centers with the strongest polarization Cδ㊀ → Iδ㊉ in HCI3, which contains well over 97% iodine.

Mechanistic Insight into Construction of Axially Chiral Biaryls via Palladium/Chiral Norbornene Cooperative Catalysis: a DFT-Based Computational Study

Catalysis Science & Technology ◽

10.1039/d1cy01863a ◽

2021 ◽

Author(s):

Xuexiang Ma ◽

Aili Feng ◽

Chengbu Liu ◽

Dongju Zhang

Keyword(s):

Density Functional ◽

Computational Study ◽

Functional Theory ◽

Cooperative Catalysis ◽

Mechanistic Insight ◽

Aryl Bromides ◽

Axially Chiral ◽

Insight Into

Density functional theory calculations were performed on a prototype of three-component reactions involving aryl iodides, 2,6-substituted aryl bromides, and acrylates to understand the construction of axially chiral biaryls through the...

Computational study on epoxidation of propylene by dioxygen using the silanol-functionalized polyoxometalate-supported osmium oxide catalyst

Inorganic Chemistry Frontiers ◽

10.1039/c9qi00900k ◽

2019 ◽

Vol 6 (12) ◽

pp. 3482-3492 ◽

Cited By ~ 2

Author(s):

Yun-Jie Chu ◽

Xue-Mei Chen ◽

Chun-Guang Liu

Keyword(s):

Density Functional ◽

Oxide Catalyst ◽

Computational Study ◽

Single Site ◽

Functional Theory ◽

Epoxidation Of Propylene ◽

Osmium Oxide

The silanol-functionalized POM-supported single-site Os oxide catalyst has been theoretically considered for epoxidation of propylene in the presence of dioxygen based on density functional theory calculations.

A computational study of hydrogen doping induced metal-to-insulator transition in CaFeO3, SrFeO3, BaFeO3 and SmMnO3

Physical Chemistry Chemical Physics ◽

10.1039/c9cp04669k ◽

2019 ◽

Vol 21 (45) ◽

pp. 25397-25405

Author(s):

Shukai Yao ◽

Pilsun Yoo ◽

Peilin Liao

Keyword(s):

Transition Metal ◽

First Principles ◽

Density Functional ◽

Computational Study ◽

Functional Theory ◽

Hydrogen Doping ◽

Gap Opening ◽

Metal To Insulator Transition

First principles density functional theory calculations were performed to identify transition metal perovskites CaFeO3, SrFeO3, BaFeO3 and SmMnO3 as promising candidates with large band gap opening upon hydrogen doping.

Homolytic bond-dissociation enthalpies of tin bonds and tin–ligand bond strengths — A computational study

Canadian Journal of Chemistry ◽

10.1139/v09-033 ◽

2009 ◽

Vol 87 (7) ◽

pp. 974-983 ◽

Cited By ~ 6

Author(s):

Sarah R. Whittleton ◽

Russell J. Boyd ◽

T. Bruce Grindley

Keyword(s):

Density Functional ◽

Computational Study ◽

Basis Set ◽

Functional Theory ◽

Bond Dissociation ◽

Donor Acceptor ◽

Bond Strengths ◽

Moller Plesset ◽

Effective Core Potentials ◽

Ligand Bond

Density functional theory and second-order Møller–Plesset perturbation theory with effective core potentials have been used to calculate homolytic bond-dissociation enthalpies, D(Sn–X), of organotin compounds, and their performance has been assessed by comparison with available experimental bond enthalpies. The SDB-aug-cc-pVTZ basis set with its effective core potential was used to calculate the D(Sn–X) of a series of trimethyltin(IV) species, Me3Sn–X, where X = H, CH3, CH2CH3, NH2, OH, Cl, and F. This is the most comprehensive report to date of homolytic Sn–X bond-dissociation enthalpies (BDEs). Effective core potentials are then used to calculate thermodynamic parameters including donor–acceptor bond enthalpies, [Formula: see text], for a series of tin-ligand complexes, L2SnX4 (X = Br or Cl, L = py, dmf, or dmtf), which are compared with previous experimental and nonrelativistic computational results. Based on computational efficiency and accuracy, it is concluded that effective core potentials are appropriate computational methods to examine bonding in organotin systems.

Computational study on redox-switchable second-order nonlinear optical properties of ferrocene-tetrathiafulvalene hybrid

RSC Advances ◽

10.1039/c4ra04548c ◽

2014 ◽

Vol 4 (72) ◽

pp. 38300-38309 ◽

Cited By ~ 7

Author(s):

Chun-Guang Liu ◽

Ming-Li Gao ◽

Zhi-Jian Wu

Keyword(s):

Optical Properties ◽

Density Functional ◽

Nonlinear Optical ◽

Computational Study ◽

Second Order ◽

Nonlinear Optical Properties ◽

Functional Theory

Redox-switchable second-order nonlinear optical (NLO) responses of a series of ferrocene-tetrathiafulvalene (Fc–TTF) hybrids have been studied based on density functional theory calculations.

ChemInform Abstract: Computational Study of Analogues of the Uranyl Ion Containing the -N=U=N- Unit: Density Functional Theory Calculations on UO22+, UON+, UN2, UO(NPH3)3+, U(NPH3)24+, [UCl4{NPR3}2] (R: H, Me), and [UOCl4{NP(C6H5)3}]-

ChemInform ◽

10.1002/chin.200108001 ◽

2001 ◽

Vol 32 (8) ◽

pp. no-no

Author(s):

Nikolas Kaltsoyannis

Keyword(s):

Density Functional ◽

Computational Study ◽

Uranyl Ion ◽

Functional Theory ◽

Unit Density

Halodiazoacetates as useful tools for selective halo-functionalization

Pure and Applied Chemistry ◽

10.1351/pac-con-10-10-18 ◽

2011 ◽

Vol 83 (3) ◽

pp. 565-575 ◽

Cited By ~ 8

Author(s):

Hanne Therese Bonge ◽

Tore Hansen

Keyword(s):

Dft Calculations ◽

Density Functional ◽

Diazo Compounds ◽

Insertion Reactions ◽

Functional Theory ◽

Kinetic Activity ◽

Synthetic Utility ◽

Insight Into ◽

Halocarbonyl Compounds

The halodiazoacetates are a group of synthetically useful halogenated diazo compounds that can be used in Rh(II)-catalyzed carbenoid reactions. In the reactions between the halodiazoacetates and electron-rich, sterically unhindered alkenes, halocyclopropanes are formed in good to excellent yields. The halodiazoacetates also react well in C–H and Si–H insertion reactions, broadening the synthetic utility of these reactions. The products of the reactions are synthetically useful α-halocarbonyl compounds. Density functional theory (DFT) calculations have given insight into the mechanism of the cyclopropanation and C–H insertion reactions of the halodiazoacetates, and have also shown that the halodiazoacetates have a particularly high kinetic activity.