Mechanochemical reactions of cocrystals: comparing theory with experiment in the making and breaking of halogen bonds in the solid state

Mechanochemical re-investigation of the halogen-bonded cocrystallization of 1,4-diazabicyclo[2.2.2]octane and 1,2-diiodotetraflurobenzene revealed an unexpectedly complex system, with three distinct cocrystal compositions, one of which also exhibits temperature-dependent polymorphism. This provided an opportunity to experimentally test the ability of dispersion-corrected periodic density functional theory (DFT) not only to explain the formation, but also predict the interconversion between halogen-bonded cocrystals of different stoichiometries,<br>

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Mechanochemical Reactions of Cocrystals: Comparing Theory with Experiment in Making and Breaking Halogen Bonds in Solid State

10.26434/chemrxiv.12153339.v1 ◽

2020 ◽

Author(s):

Filip Topic ◽

Mihails Arhangelskis ◽

Poppy Hindle ◽

Ricky Tran ◽

Andrew Morris ◽

...

Keyword(s):

Complex System ◽

Density Functional Theory ◽

Solid State ◽

Density Functional ◽

Halogen Bonds ◽

Temperature Dependent ◽

Functional Theory ◽

Mechanochemical Reactions

Mechanochemical re-investigation of the halogen-bonded cocrystallization of 1,4-diazabicyclo[2.2.2]octane and 1,2-diiodotetraflurobenzene revealed an unexpectedly complex system, with three distinct cocrystal compositions, one of which also exhibits temperature-dependent polymorphism. This provided an opportunity to experimentally test the ability of dispersion-corrected periodic density functional theory (DFT) not only to explain the formation, but also predict the interconversion between halogen-bonded cocrystals of different stoichiometries,<br>

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Iron(II) complexes of dimethyltriazacyclophane

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229618015255 ◽

2018 ◽

Vol 74 (12) ◽

pp. 1641-1649

Author(s):

Wei-Tsung Lee ◽

Matthias Zeller ◽

David Upp ◽

Yuliya Politanska ◽

Doug Steinman ◽

...

Keyword(s):

Density Functional Theory ◽

Solid State ◽

Dft Calculations ◽

Density Functional Calculations ◽

Density Functional ◽

Coordination Mode ◽

Functional Theory ◽

Metal Centers ◽

Bonding Interaction

Treatment of the ortho-triazacyclophane 1,4-dimethyltribenzo[b,e,h][1,4,7]triazacyclonona-2,5,8-triene [(C6H5)3(NH)(NCH3)2, L1] with Fe[N(SiMe3)2]2 yields the dimeric iron(II) complex bis(μ-1,4-dimethyltribenzo[b,e,h][1,4,7]triazacyclonona-2,5,8-trien-7-ido)bis[(μ-1,4-dimethyltribenzo[b,e,h][1,4,7]triazacyclonona-2,5,8-trien-7-ido)iron(II)], [Fe(C20H18N3)4] or Fe2(L1)4 (9). Dissolution of 9 in tetrahydrofuran (THF) results in solvation by two THF ligands and the formation of a simpler monoiron complex, namely bis(μ-1,4-dimethyltribenzo[b,e,h][1,4,7]triazacyclonona-2,5,8-trien-7-ido-κN 7)bis(tetrahydrofuran-κO)iron(II), [Fe(C20H18N3)2(C4H8O)2] or (L1)2Fe(THF)2 (10). The reaction is reversible and 10 reverts in vacuo to diiron complex 9. In the structures of both 9 and 10, the monoanionic triazacyclophane ligand L1− is observed in only the less-symmetric saddle conformation. No bowl-shaped crown conformers are observed in the solid state, thus preventing chelating κ3-coordination to the metal as had been proposed earlier based on density functional theory (DFT) calculations. Instead, the L1− ligands are bound in either a η2-chelating fashion through the amide and one amine donor (for one of the four ligands of 9), or solely through their amide N atoms in an even simpler monodentate η1-coordination mode. Density functional calculations on dimer 9 revealed nearly full cationic charges on each Fe atom and no bonding interaction between the two metal centers, consistent with the relatively long Fe...Fe distance of 2.912 (1) Å observed in the solid state.

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CO2 activation through silylimido and silylamido zirconium hydrides supported on N-donor chelating SBA15 surface ligands

Chemical Communications ◽

10.1039/c5cc08821f ◽

2016 ◽

Vol 52 (12) ◽

pp. 2577-2580 ◽

Cited By ~ 8

Author(s):

Farhan Ahmad Pasha ◽

Anissa Bendjeriou-Sedjerari ◽

Edy Abou-Hamad ◽

Kuo-Wei Huang ◽

Jean-Marie Basset

Keyword(s):

Density Functional Theory ◽

Solid State ◽

Solid State Nmr ◽

Density Functional ◽

Density Functional Theory Calculations ◽

Co2 Activation ◽

Functional Theory ◽

Surface Ligands ◽

Different Types ◽

Zirconium Hydrides

Density functional theory calculations and 2D 1H–13C HETCOR solid state NMR spectroscopy prove that CO2 can be used to probe, by its own reactivity, different types of N-donor surface ligands on SBA15-supported ZrIV hydrides: [(Si–O–)(Si–N)[Zr]H] and [(Si–NH–)(Si–X–)[Zr]H2] (XO or NH).

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Substituent Effects in 3,3’ Bipyrazole Derivatives. X-ray Crystal Structures, Molecular Properties and DFT Analysis

Acta Chimica Slovenica ◽

10.17344/acsi.2021.6756 ◽

2021 ◽

Vol 68 (3) ◽

pp. 718-727

Author(s):

Ibrahim Bouabdallah ◽

Tarik Harit ◽

Mahmoud Rahal ◽

Fouad Malek ◽

Monique Tillard ◽

...

Keyword(s):

Crystal Structure ◽

Density Functional Theory ◽

Solid State ◽

Dft Calculations ◽

Single Crystal ◽

Crystal Structures ◽

Density Functional ◽

Substituent Effects ◽

Functional Theory ◽

X Ray

The single crystal X-ray structure of new 1,1’-bis(2-nitrophenyl)-5,5’-diisopropyl-3,3’-bipyrazole, 1, is triclinic P I–, a = 7.7113(8), b = 12.3926(14), c = 12.9886(12) Å, α = 92.008(8), β = 102.251(8), γ = 99.655(9)°. The structural arrangement is compared to that of 5,5’-diisopropyl-3,3’-bipyrazole, 5, whose single crystal structure is found tetragonal I41/a, a = b = 11.684(1), c = 19.158(1) Å. The comparison is also extended to the structures previously determined for 1,1’-bis(2-nitrophenyl)-5,5’-propyl-3,3’-bipyrazole, 2, 1,1’-bis(4-nitrophenyl)-5,5’-diisopropyl-3,3’-bipyrazole, 3, and 1,1’-bis(benzyl)-5,5’-diisopropyl-3,3’-bipyrazole, 4. Density Functional Theory (DFT) calculations are used to investigate the molecular geometries and to determine the global reactivity parameters. The geometry of isolated molecules and the molecular arrangements in the solid state are analyzed according to the nature of the groups connected to the bipyrazole core.

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Development of transition-metal-catalyzed cycloaddition reactions leading to polycarbocyclic systems

Pure and Applied Chemistry ◽

10.1351/pac-con-10-10-23 ◽

2011 ◽

Vol 83 (3) ◽

pp. 495-506 ◽

Cited By ~ 41

Author(s):

Moisés Gulías ◽

Fernando López ◽

José L. Mascareñas

Keyword(s):

Density Functional Theory ◽

Transition Metal ◽

Dft Calculations ◽

Density Functional ◽

Conjugated Dienes ◽

Ni Catalysts ◽

Functional Theory ◽

Different Types ◽

Transition Metal Catalyzed ◽

Metal Catalyzed

We present a compilation of methodologies developed in our laboratories to assemble polycyclic structures containing small- and medium-sized cycles, relying on the use of transition-metal-catalyzed (TMC) cycloadditions. First, we discuss the use of alkylidenecyclopropanes (ACPs) as 3C-atom partners, in particular in their Pd-catalyzed (3 + 2) cycloadditions with alkynes, alkenes, and allenes, reactions that lead to cyclopentane-containing polycyclic products in excellent yields. Then, we present the expansion of this chemistry to a (4 + 3) annulation with conjugated dienes, and to inter- and intramolecular (3 + 2 + 2) cycloadditions using external alkenes as additional 2C-π-systems. These reactions allow the preparation of different types of polycyclic structures containing cycloheptene rings, the topology of the products depending on the use of Pd or Ni catalysts. Finally, we include our more recent discoveries on the development of (4 + 3) and (4 + 2) intramolecular cyclo-additions of allenes and dienes, promoted by Pt and Au catalysts, and discuss mechanistic insights supported by experimental and density functional theory (DFT) calculations. An enantioselective version of the (4 + 2) cycloaddition with phosphoramidite Au(I) catalysts is also presented.

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Syntheses, crystal structures and density functional theory investigations of copper(ii) complexes bearing tridentate Schiff base ligands derived from 8-aminoquinoline

CrystEngComm ◽

10.1039/c5ce00809c ◽

2015 ◽

Vol 17 (30) ◽

pp. 5664-5671 ◽

Cited By ~ 10

Author(s):

Prasanta Kumar Bhaumik ◽

Antonio Bauzá ◽

Michael G. B. Drew ◽

Antonio Frontera ◽

Shouvik Chattopadhyay

Keyword(s):

Density Functional Theory ◽

Schiff Base ◽

Solid State ◽

Dft Calculations ◽

Crystal Structures ◽

Density Functional ◽

Schiff Base Complexes ◽

Schiff Base Ligands ◽

Functional Theory ◽

Tridentate Schiff Base

Three copper(ii) Schiff base complexes have been synthesized and characterized. Supramolecular assemblies in the solid state are analyzed by DFT calculations.

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Theoretical investigation of interactions between palladium and fullerene in polymer

RSC Advances ◽

10.1039/c6ra24822e ◽

2017 ◽

Vol 7 (4) ◽

pp. 2202-2210 ◽

Cited By ~ 13

Author(s):

Jakub Goclon ◽

Krzysztof Winkler ◽

Johannes T. Margraf

Keyword(s):

Density Functional Theory ◽

Dft Calculations ◽

Electronic Properties ◽

Theoretical Investigation ◽

Density Functional ◽

Functional Theory ◽

Structural And Electronic Properties ◽

Different Types ◽

Fullerene Polymers

Applying density functional theory (DFT) calculations, we predict the structural and electronic properties of different types of palladium–fullerene polymers.

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