New rhenium-tricarbonyl complexes bearing halogen-substituted bidentate ligands: Structural, computational and Hirshfeld surfaces studies

Reza Kia, Soheil Mahmoudi, Paul Raithby

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Abstract

A series of ten rhenium tricarbonyl complexes (C1-C10), bearing halogen-substituted bidentate N,N-donor ligands with halogens or trifluoromethyl groups (X = –F, –Cl, –Br, and –CF3) in different positions on the aromatic rings were synthesized and characterized by FT-IR and 1H-NMR spectroscopy and their solid-state structures were determined by single crystal X-ray diffraction. The resultant complexes Re(CO)3(N,N)X display an octahedral coordination geometry around the central Re atom, and in all the complexes the Re(CO)3 unit adopts a fac geometry. The metal-bound halogen atoms along with the halogen-substituted ligands were used to fine-tune the electron density of the halogen σ-hole on the coordinated halide that is involved in halogen-halogen and other intermolecular interactions. This series of compounds was used to explore the range of possible intermolecular involving rhenium coordinated halides. These supramolecular interactions include: (i) halogen bonding through metal-bound halogen with carbon-bound halogen (Re–X…X–C) (ii) halogen bonding through carbon-bound halogen with carbon-bound halogen (C–X…X–C) (iii) dipolar interactions through carbonyl-carbonyl (CO…CO) (iv) C–H…X hydrogen bonding interactions (v) C–H…O hydrogen bonding interactions (vi) halogen (X)…heteroatom (N, O) interactions and (vii) metal-bond carbonyl lone pair with aromatic π-ring interaction, Re–CO(lone pair)…π (aromatic ring). In each case the molecular electrostatic potential and non-covalent interaction index were calculated. Crystal packing analyses using Hirshfeld surface calculation confirmed that metal-bound halogen is more effective than carbon-bound halogen in the formation of intermolecular interactions. Complexes C8 and C10 featured interesting intramolecular Re–CO(lone pair)…π interactions, the presence of which were confirmed by molecular orbital and non-covalent interaction index (NCI) calculations.
LanguageEnglish
JournalCrystEngComm
Early online date4 Dec 2018
DOIs
StatusE-pub ahead of print - 4 Dec 2018

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{10de413c74574922a1f835e91a071ac8,
title = "New rhenium-tricarbonyl complexes bearing halogen-substituted bidentate ligands: Structural, computational and Hirshfeld surfaces studies",
abstract = "A series of ten rhenium tricarbonyl complexes (C1-C10), bearing halogen-substituted bidentate N,N-donor ligands with halogens or trifluoromethyl groups (X = –F, –Cl, –Br, and –CF3) in different positions on the aromatic rings were synthesized and characterized by FT-IR and 1H-NMR spectroscopy and their solid-state structures were determined by single crystal X-ray diffraction. The resultant complexes Re(CO)3(N,N)X display an octahedral coordination geometry around the central Re atom, and in all the complexes the Re(CO)3 unit adopts a fac geometry. The metal-bound halogen atoms along with the halogen-substituted ligands were used to fine-tune the electron density of the halogen σ-hole on the coordinated halide that is involved in halogen-halogen and other intermolecular interactions. This series of compounds was used to explore the range of possible intermolecular involving rhenium coordinated halides. These supramolecular interactions include: (i) halogen bonding through metal-bound halogen with carbon-bound halogen (Re–X…X–C) (ii) halogen bonding through carbon-bound halogen with carbon-bound halogen (C–X…X–C) (iii) dipolar interactions through carbonyl-carbonyl (CO…CO) (iv) C–H…X hydrogen bonding interactions (v) C–H…O hydrogen bonding interactions (vi) halogen (X)…heteroatom (N, O) interactions and (vii) metal-bond carbonyl lone pair with aromatic π-ring interaction, Re–CO(lone pair)…π (aromatic ring). In each case the molecular electrostatic potential and non-covalent interaction index were calculated. Crystal packing analyses using Hirshfeld surface calculation confirmed that metal-bound halogen is more effective than carbon-bound halogen in the formation of intermolecular interactions. Complexes C8 and C10 featured interesting intramolecular Re–CO(lone pair)…π interactions, the presence of which were confirmed by molecular orbital and non-covalent interaction index (NCI) calculations.",
author = "Reza Kia and Soheil Mahmoudi and Paul Raithby",
year = "2018",
month = "12",
day = "4",
doi = "10.1039/C8CE01860J",
language = "English",
journal = "CrystEngComm",
issn = "1466-8033",
publisher = "Royal Society of Chemistry",

}

TY - JOUR

T1 - New rhenium-tricarbonyl complexes bearing halogen-substituted bidentate ligands: Structural, computational and Hirshfeld surfaces studies

AU - Kia, Reza

AU - Mahmoudi, Soheil

AU - Raithby, Paul

PY - 2018/12/4

Y1 - 2018/12/4

N2 - A series of ten rhenium tricarbonyl complexes (C1-C10), bearing halogen-substituted bidentate N,N-donor ligands with halogens or trifluoromethyl groups (X = –F, –Cl, –Br, and –CF3) in different positions on the aromatic rings were synthesized and characterized by FT-IR and 1H-NMR spectroscopy and their solid-state structures were determined by single crystal X-ray diffraction. The resultant complexes Re(CO)3(N,N)X display an octahedral coordination geometry around the central Re atom, and in all the complexes the Re(CO)3 unit adopts a fac geometry. The metal-bound halogen atoms along with the halogen-substituted ligands were used to fine-tune the electron density of the halogen σ-hole on the coordinated halide that is involved in halogen-halogen and other intermolecular interactions. This series of compounds was used to explore the range of possible intermolecular involving rhenium coordinated halides. These supramolecular interactions include: (i) halogen bonding through metal-bound halogen with carbon-bound halogen (Re–X…X–C) (ii) halogen bonding through carbon-bound halogen with carbon-bound halogen (C–X…X–C) (iii) dipolar interactions through carbonyl-carbonyl (CO…CO) (iv) C–H…X hydrogen bonding interactions (v) C–H…O hydrogen bonding interactions (vi) halogen (X)…heteroatom (N, O) interactions and (vii) metal-bond carbonyl lone pair with aromatic π-ring interaction, Re–CO(lone pair)…π (aromatic ring). In each case the molecular electrostatic potential and non-covalent interaction index were calculated. Crystal packing analyses using Hirshfeld surface calculation confirmed that metal-bound halogen is more effective than carbon-bound halogen in the formation of intermolecular interactions. Complexes C8 and C10 featured interesting intramolecular Re–CO(lone pair)…π interactions, the presence of which were confirmed by molecular orbital and non-covalent interaction index (NCI) calculations.

AB - A series of ten rhenium tricarbonyl complexes (C1-C10), bearing halogen-substituted bidentate N,N-donor ligands with halogens or trifluoromethyl groups (X = –F, –Cl, –Br, and –CF3) in different positions on the aromatic rings were synthesized and characterized by FT-IR and 1H-NMR spectroscopy and their solid-state structures were determined by single crystal X-ray diffraction. The resultant complexes Re(CO)3(N,N)X display an octahedral coordination geometry around the central Re atom, and in all the complexes the Re(CO)3 unit adopts a fac geometry. The metal-bound halogen atoms along with the halogen-substituted ligands were used to fine-tune the electron density of the halogen σ-hole on the coordinated halide that is involved in halogen-halogen and other intermolecular interactions. This series of compounds was used to explore the range of possible intermolecular involving rhenium coordinated halides. These supramolecular interactions include: (i) halogen bonding through metal-bound halogen with carbon-bound halogen (Re–X…X–C) (ii) halogen bonding through carbon-bound halogen with carbon-bound halogen (C–X…X–C) (iii) dipolar interactions through carbonyl-carbonyl (CO…CO) (iv) C–H…X hydrogen bonding interactions (v) C–H…O hydrogen bonding interactions (vi) halogen (X)…heteroatom (N, O) interactions and (vii) metal-bond carbonyl lone pair with aromatic π-ring interaction, Re–CO(lone pair)…π (aromatic ring). In each case the molecular electrostatic potential and non-covalent interaction index were calculated. Crystal packing analyses using Hirshfeld surface calculation confirmed that metal-bound halogen is more effective than carbon-bound halogen in the formation of intermolecular interactions. Complexes C8 and C10 featured interesting intramolecular Re–CO(lone pair)…π interactions, the presence of which were confirmed by molecular orbital and non-covalent interaction index (NCI) calculations.

U2 - 10.1039/C8CE01860J

DO - 10.1039/C8CE01860J

M3 - Article

JO - CrystEngComm

T2 - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

ER -