Synthesis, structure and theoretical investigation into a homoleptic tris(dithiolene) tungsten

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Abstract

A new homoleptic dithiolene tungsten complex, tris-{1,2-bis(3,5- dimethoxyphenyl)-1,2-ethylenodithiolene-S,S′}tungsten, was successfully synthesized via a reaction of the thiophosphate ester and sodium tungstate. The thiophosphate ester was prepared from 3,5-dimethoxybenzaldehyde via benzoin condensation to produce the intermediate 1,2-bis-(3,5-dimethoxyphenyl)-2- hydroxy-ethanone compound, followed by a reaction of the intermediate with phosphorus pentasulfide. FTIR, UV-Vis spectroscopy, 1H NMR and 13C NMR and elemental analysis confirmed the product as tris{1,2-bis-(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S′}tungsten with the molecular formula of C54H54O12S 6W. Crystals of the product adopted a monoclinic system with space group of P2(1)/n, where a = 12.756(2) Å, b = 21.560(3) Å, c = 24.980(4) Å and β = 103.998(3). Three thioester ligands were attached to the tungsten as bidentate chelates to form a distorted octahedral geometry. Density functional theory calculations were performed to investigate the molecular properties in a generalized-gradient approximation framework system using Perdew-Burke-Ernzerhof functions and a double numeric plus polarization basis set. The HOMO was concentrated on the phenyl ligands, while the LUMO was found along the W(S2C2)3 rings. The theoretical optical properties showed a slight blue shift in several low dielectric solvents. The solvatochromism effect was insignificant for high polar solvents.

Original languageEnglish
Pages (from-to)208-215
Number of pages8
JournalSpectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
Volume120
DOIs
Publication statusPublished - 2014

Fingerprint

Tungsten
tungsten
synthesis
esters
Esters
Benzoin
Ligands
Nuclear magnetic resonance
nuclear magnetic resonance
ligands
tungstates
molecular properties
products
Ultraviolet spectroscopy
chelates
blue shift
Density functional theory
phosphorus
Phosphorus
Condensation

Keywords

  • DFT
  • Dithiolene
  • Homoleptic
  • Non-innocent
  • Tungsten

ASJC Scopus subject areas

  • Instrumentation
  • Atomic and Molecular Physics, and Optics
  • Analytical Chemistry
  • Spectroscopy

Cite this

@article{54652172bc014a44a2572c0e2da6e384,
title = "Synthesis, structure and theoretical investigation into a homoleptic tris(dithiolene) tungsten",
abstract = "A new homoleptic dithiolene tungsten complex, tris-{1,2-bis(3,5- dimethoxyphenyl)-1,2-ethylenodithiolene-S,S′}tungsten, was successfully synthesized via a reaction of the thiophosphate ester and sodium tungstate. The thiophosphate ester was prepared from 3,5-dimethoxybenzaldehyde via benzoin condensation to produce the intermediate 1,2-bis-(3,5-dimethoxyphenyl)-2- hydroxy-ethanone compound, followed by a reaction of the intermediate with phosphorus pentasulfide. FTIR, UV-Vis spectroscopy, 1H NMR and 13C NMR and elemental analysis confirmed the product as tris{1,2-bis-(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S′}tungsten with the molecular formula of C54H54O12S 6W. Crystals of the product adopted a monoclinic system with space group of P2(1)/n, where a = 12.756(2) {\AA}, b = 21.560(3) {\AA}, c = 24.980(4) {\AA} and β = 103.998(3). Three thioester ligands were attached to the tungsten as bidentate chelates to form a distorted octahedral geometry. Density functional theory calculations were performed to investigate the molecular properties in a generalized-gradient approximation framework system using Perdew-Burke-Ernzerhof functions and a double numeric plus polarization basis set. The HOMO was concentrated on the phenyl ligands, while the LUMO was found along the W(S2C2)3 rings. The theoretical optical properties showed a slight blue shift in several low dielectric solvents. The solvatochromism effect was insignificant for high polar solvents.",
keywords = "DFT, Dithiolene, Homoleptic, Non-innocent, Tungsten",
author = "Arifin Khuzaimah and {Effery Minggu}, Lorna and {Wan Daud}, {Wan Ramli} and {Mohd. Yamin}, Bohari and Rusli Daik and Mohammad Kassim",
year = "2014",
doi = "10.1016/j.saa.2013.09.069",
language = "English",
volume = "120",
pages = "208--215",
journal = "Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy",
issn = "1386-1425",
publisher = "Elsevier",

}

TY - JOUR

T1 - Synthesis, structure and theoretical investigation into a homoleptic tris(dithiolene) tungsten

AU - Khuzaimah, Arifin

AU - Effery Minggu, Lorna

AU - Wan Daud, Wan Ramli

AU - Mohd. Yamin, Bohari

AU - Daik, Rusli

AU - Kassim, Mohammad

PY - 2014

Y1 - 2014

N2 - A new homoleptic dithiolene tungsten complex, tris-{1,2-bis(3,5- dimethoxyphenyl)-1,2-ethylenodithiolene-S,S′}tungsten, was successfully synthesized via a reaction of the thiophosphate ester and sodium tungstate. The thiophosphate ester was prepared from 3,5-dimethoxybenzaldehyde via benzoin condensation to produce the intermediate 1,2-bis-(3,5-dimethoxyphenyl)-2- hydroxy-ethanone compound, followed by a reaction of the intermediate with phosphorus pentasulfide. FTIR, UV-Vis spectroscopy, 1H NMR and 13C NMR and elemental analysis confirmed the product as tris{1,2-bis-(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S′}tungsten with the molecular formula of C54H54O12S 6W. Crystals of the product adopted a monoclinic system with space group of P2(1)/n, where a = 12.756(2) Å, b = 21.560(3) Å, c = 24.980(4) Å and β = 103.998(3). Three thioester ligands were attached to the tungsten as bidentate chelates to form a distorted octahedral geometry. Density functional theory calculations were performed to investigate the molecular properties in a generalized-gradient approximation framework system using Perdew-Burke-Ernzerhof functions and a double numeric plus polarization basis set. The HOMO was concentrated on the phenyl ligands, while the LUMO was found along the W(S2C2)3 rings. The theoretical optical properties showed a slight blue shift in several low dielectric solvents. The solvatochromism effect was insignificant for high polar solvents.

AB - A new homoleptic dithiolene tungsten complex, tris-{1,2-bis(3,5- dimethoxyphenyl)-1,2-ethylenodithiolene-S,S′}tungsten, was successfully synthesized via a reaction of the thiophosphate ester and sodium tungstate. The thiophosphate ester was prepared from 3,5-dimethoxybenzaldehyde via benzoin condensation to produce the intermediate 1,2-bis-(3,5-dimethoxyphenyl)-2- hydroxy-ethanone compound, followed by a reaction of the intermediate with phosphorus pentasulfide. FTIR, UV-Vis spectroscopy, 1H NMR and 13C NMR and elemental analysis confirmed the product as tris{1,2-bis-(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S′}tungsten with the molecular formula of C54H54O12S 6W. Crystals of the product adopted a monoclinic system with space group of P2(1)/n, where a = 12.756(2) Å, b = 21.560(3) Å, c = 24.980(4) Å and β = 103.998(3). Three thioester ligands were attached to the tungsten as bidentate chelates to form a distorted octahedral geometry. Density functional theory calculations were performed to investigate the molecular properties in a generalized-gradient approximation framework system using Perdew-Burke-Ernzerhof functions and a double numeric plus polarization basis set. The HOMO was concentrated on the phenyl ligands, while the LUMO was found along the W(S2C2)3 rings. The theoretical optical properties showed a slight blue shift in several low dielectric solvents. The solvatochromism effect was insignificant for high polar solvents.

KW - DFT

KW - Dithiolene

KW - Homoleptic

KW - Non-innocent

KW - Tungsten

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U2 - 10.1016/j.saa.2013.09.069

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JO - Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy

JF - Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy

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