Tungsten(VI) N-heterocyclic carbene complexes: synthetic, structural, and computational study

Research output: Contribution to journalArticle

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Abstract

The reaction of WOCl4 with 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (Idipp) leads to an orange solid whose spectroscopic data are consistent with the 1:1 adduct [WOCl4(Idipp)]. Computational studies at the DFT level further support this formulation. Exposure of this compound to the atmosphere results in rapid hydrolysis to various imidazolium salts. If air diffuses very slowly into solutions of [WOCl4(Idipp)], it also undergoes slow hydrolysis to form [WO2Cl2(Idipp)]. This has been crystallographically characterized and is the first five-coordinate, 1:1 adduct of WO2Cl2. This complex has also been subject to DFT calculations, and its metal-ligand bonding has been explored. The carbene-metal interaction is primarily σ-donor in nature. The mechanism of the hydrolysis has also been probed by computational methods, revealing a plausible, low-energy reaction pathway.

LanguageEnglish
Pages6262–6269
Number of pages8
JournalOrganometallics
Volume30
Issue number22
Early online date3 Nov 2011
DOIs
Publication statusPublished - 28 Nov 2011

Fingerprint

Tungsten
carbenes
hydrolysis
Hydrolysis
tungsten
Discrete Fourier transforms
adducts
Metals
Computational methods
imidazoles
metals
Salts
Ligands
salts
formulations
atmospheres
ligands
air
Air
carbene

Keywords

  • carbene complexes
  • N-heterocyclic carbene complexes
  • organometallics
  • synthetic
  • structural
  • computational study

Cite this

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title = "Tungsten(VI) N-heterocyclic carbene complexes: synthetic, structural, and computational study",
abstract = "The reaction of WOCl4 with 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (Idipp) leads to an orange solid whose spectroscopic data are consistent with the 1:1 adduct [WOCl4(Idipp)]. Computational studies at the DFT level further support this formulation. Exposure of this compound to the atmosphere results in rapid hydrolysis to various imidazolium salts. If air diffuses very slowly into solutions of [WOCl4(Idipp)], it also undergoes slow hydrolysis to form [WO2Cl2(Idipp)]. This has been crystallographically characterized and is the first five-coordinate, 1:1 adduct of WO2Cl2. This complex has also been subject to DFT calculations, and its metal-ligand bonding has been explored. The carbene-metal interaction is primarily σ-donor in nature. The mechanism of the hydrolysis has also been probed by computational methods, revealing a plausible, low-energy reaction pathway.",
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Tungsten(VI) N-heterocyclic carbene complexes : synthetic, structural, and computational study. / Dodds, Christopher A; Spicer, Mark D; Tuttle, Tell.

In: Organometallics, Vol. 30, No. 22, 28.11.2011, p. 6262–6269.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Tungsten(VI) N-heterocyclic carbene complexes

T2 - Organometallics

AU - Dodds, Christopher A

AU - Spicer, Mark D

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Y1 - 2011/11/28

N2 - The reaction of WOCl4 with 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (Idipp) leads to an orange solid whose spectroscopic data are consistent with the 1:1 adduct [WOCl4(Idipp)]. Computational studies at the DFT level further support this formulation. Exposure of this compound to the atmosphere results in rapid hydrolysis to various imidazolium salts. If air diffuses very slowly into solutions of [WOCl4(Idipp)], it also undergoes slow hydrolysis to form [WO2Cl2(Idipp)]. This has been crystallographically characterized and is the first five-coordinate, 1:1 adduct of WO2Cl2. This complex has also been subject to DFT calculations, and its metal-ligand bonding has been explored. The carbene-metal interaction is primarily σ-donor in nature. The mechanism of the hydrolysis has also been probed by computational methods, revealing a plausible, low-energy reaction pathway.

AB - The reaction of WOCl4 with 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (Idipp) leads to an orange solid whose spectroscopic data are consistent with the 1:1 adduct [WOCl4(Idipp)]. Computational studies at the DFT level further support this formulation. Exposure of this compound to the atmosphere results in rapid hydrolysis to various imidazolium salts. If air diffuses very slowly into solutions of [WOCl4(Idipp)], it also undergoes slow hydrolysis to form [WO2Cl2(Idipp)]. This has been crystallographically characterized and is the first five-coordinate, 1:1 adduct of WO2Cl2. This complex has also been subject to DFT calculations, and its metal-ligand bonding has been explored. The carbene-metal interaction is primarily σ-donor in nature. The mechanism of the hydrolysis has also been probed by computational methods, revealing a plausible, low-energy reaction pathway.

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KW - N-heterocyclic carbene complexes

KW - organometallics

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KW - structural

KW - computational study

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