Arene-polyfluoroarene π-π stacking between N-heterocyclic carbene ligands of pentamethylcyclopentadienyl group 9 metal complexes

Alistair J. Lockley, Andrew C. Marr, Graham C. Saunders, Hayden P. Thomas

Research output: Contribution to journalArticle

Abstract

(η5-Pentamethylcyclopentadienyl)rhodium(κC-1-(2,3,4,5,6-pentafluorophenylmethyl)-3-benzylimidazol-2-ylidene) dichloride (1a) and its iridium analogue (1b) crystallize as dichloromethane solvates in the enantiomorphous space group P212121. (η5-Pentamethylcyclopentadienyl)rhodium(κC-1-(4-trifluoromethyl-2,3,5,6-tetrafluorophenylmethyl)-3-benzylimidazol-2-ylidene) dichloride (2a) and its iridium analogue (2b) crystallize as dichloromethane solvates in the polar space group Pca21. All the crystal structures possess columns of alternating complex and dichloromethane molecules which are linked by hydrogen bonding. Perpendicular to these is hydrogen bonding between the imidazol-2-ylidene hydrogen atoms and chloride ligands. The crystal structures of 2a and 2b also display intermolecular π–π stacking between the phenyl and trifluoromethyltetrafluorophenyl rings of molecules in a direction perpendicular to the columns and hydrogen bonding between the complex molecules. In contrast those of 1a and 1b display intermolecular lone pair–π interactions in the same direction as the hydrogen bonding between the complex molecules. DFT calculations reveal that the π–π stacking and lone pair–π interactions are of approximately the same energy. The difference in the structures arises from the steric requirements of the trifluoromethyl group.
Original languageEnglish
JournalJournal of Fluorine Chemistry
Early online date25 Jan 2019
DOIs
Publication statusEarly online date - 25 Jan 2019

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Coordination Complexes
carbenes
Hydrogen Bonding
stacking
ligand
Methylene Chloride
Hydrogen bonds
hydrogen
Ligands
Iridium
Rhodium
ligands
Molecules
dichlorides
metal
rhodium
iridium
metals
molecules
crystal structure

Cite this

@article{f95123f0d3d742acae22bbb08e72e636,
title = "Arene-polyfluoroarene π-π stacking between N-heterocyclic carbene ligands of pentamethylcyclopentadienyl group 9 metal complexes",
abstract = "(η5-Pentamethylcyclopentadienyl)rhodium(κC-1-(2,3,4,5,6-pentafluorophenylmethyl)-3-benzylimidazol-2-ylidene) dichloride (1a) and its iridium analogue (1b) crystallize as dichloromethane solvates in the enantiomorphous space group P212121. (η5-Pentamethylcyclopentadienyl)rhodium(κC-1-(4-trifluoromethyl-2,3,5,6-tetrafluorophenylmethyl)-3-benzylimidazol-2-ylidene) dichloride (2a) and its iridium analogue (2b) crystallize as dichloromethane solvates in the polar space group Pca21. All the crystal structures possess columns of alternating complex and dichloromethane molecules which are linked by hydrogen bonding. Perpendicular to these is hydrogen bonding between the imidazol-2-ylidene hydrogen atoms and chloride ligands. The crystal structures of 2a and 2b also display intermolecular π–π stacking between the phenyl and trifluoromethyltetrafluorophenyl rings of molecules in a direction perpendicular to the columns and hydrogen bonding between the complex molecules. In contrast those of 1a and 1b display intermolecular lone pair–π interactions in the same direction as the hydrogen bonding between the complex molecules. DFT calculations reveal that the π–π stacking and lone pair–π interactions are of approximately the same energy. The difference in the structures arises from the steric requirements of the trifluoromethyl group.",
author = "Lockley, {Alistair J.} and Marr, {Andrew C.} and Saunders, {Graham C.} and Thomas, {Hayden P.}",
year = "2019",
month = "1",
day = "25",
doi = "10.1016/j.jfluchem.2019.01.006",
language = "English",
journal = "Journal of Fluorine Chemistry",
issn = "0022-1139",
publisher = "Elsevier",

}

Arene-polyfluoroarene π-π stacking between N-heterocyclic carbene ligands of pentamethylcyclopentadienyl group 9 metal complexes. / Lockley, Alistair J.; Marr, Andrew C.; Saunders, Graham C.; Thomas, Hayden P.

In: Journal of Fluorine Chemistry, 25.01.2019.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Arene-polyfluoroarene π-π stacking between N-heterocyclic carbene ligands of pentamethylcyclopentadienyl group 9 metal complexes

AU - Lockley, Alistair J.

AU - Marr, Andrew C.

AU - Saunders, Graham C.

AU - Thomas, Hayden P.

PY - 2019/1/25

Y1 - 2019/1/25

N2 - (η5-Pentamethylcyclopentadienyl)rhodium(κC-1-(2,3,4,5,6-pentafluorophenylmethyl)-3-benzylimidazol-2-ylidene) dichloride (1a) and its iridium analogue (1b) crystallize as dichloromethane solvates in the enantiomorphous space group P212121. (η5-Pentamethylcyclopentadienyl)rhodium(κC-1-(4-trifluoromethyl-2,3,5,6-tetrafluorophenylmethyl)-3-benzylimidazol-2-ylidene) dichloride (2a) and its iridium analogue (2b) crystallize as dichloromethane solvates in the polar space group Pca21. All the crystal structures possess columns of alternating complex and dichloromethane molecules which are linked by hydrogen bonding. Perpendicular to these is hydrogen bonding between the imidazol-2-ylidene hydrogen atoms and chloride ligands. The crystal structures of 2a and 2b also display intermolecular π–π stacking between the phenyl and trifluoromethyltetrafluorophenyl rings of molecules in a direction perpendicular to the columns and hydrogen bonding between the complex molecules. In contrast those of 1a and 1b display intermolecular lone pair–π interactions in the same direction as the hydrogen bonding between the complex molecules. DFT calculations reveal that the π–π stacking and lone pair–π interactions are of approximately the same energy. The difference in the structures arises from the steric requirements of the trifluoromethyl group.

AB - (η5-Pentamethylcyclopentadienyl)rhodium(κC-1-(2,3,4,5,6-pentafluorophenylmethyl)-3-benzylimidazol-2-ylidene) dichloride (1a) and its iridium analogue (1b) crystallize as dichloromethane solvates in the enantiomorphous space group P212121. (η5-Pentamethylcyclopentadienyl)rhodium(κC-1-(4-trifluoromethyl-2,3,5,6-tetrafluorophenylmethyl)-3-benzylimidazol-2-ylidene) dichloride (2a) and its iridium analogue (2b) crystallize as dichloromethane solvates in the polar space group Pca21. All the crystal structures possess columns of alternating complex and dichloromethane molecules which are linked by hydrogen bonding. Perpendicular to these is hydrogen bonding between the imidazol-2-ylidene hydrogen atoms and chloride ligands. The crystal structures of 2a and 2b also display intermolecular π–π stacking between the phenyl and trifluoromethyltetrafluorophenyl rings of molecules in a direction perpendicular to the columns and hydrogen bonding between the complex molecules. In contrast those of 1a and 1b display intermolecular lone pair–π interactions in the same direction as the hydrogen bonding between the complex molecules. DFT calculations reveal that the π–π stacking and lone pair–π interactions are of approximately the same energy. The difference in the structures arises from the steric requirements of the trifluoromethyl group.

U2 - 10.1016/j.jfluchem.2019.01.006

DO - 10.1016/j.jfluchem.2019.01.006

M3 - Article

JO - Journal of Fluorine Chemistry

JF - Journal of Fluorine Chemistry

SN - 0022-1139

ER -