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

Christopher A. Dodds; Mark D. Spicer; Tell Tuttle

doi:10.1021/om200838f

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

Christopher A. Dodds, Mark D. Spicer^*, Tell Tuttle

^*Corresponding author for this work

Chemical Science

Research output: Contribution to journal › Article › peer-review

19 Citations (Scopus)

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.

Original language	English
Pages (from-to)	6262-6269
Number of pages	8
Journal	Organometallics
Volume	30
Issue number	22
Early online date	3 Nov 2011
DOIs	https://doi.org/10.1021/om200838f
Publication status	Published - 28 Nov 2011

Keywords

adducts
carbene compounds
ligands
metals
molecular structure

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

Documents and Links

10.1021/om200838f

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.",

keywords = "adducts, carbene compounds, ligands, metals, molecular structure",

author = "Dodds, {Christopher A.} and Spicer, {Mark D.} and Tell Tuttle",

year = "2011",

month = nov,

day = "28",

doi = "10.1021/om200838f",

language = "English",

volume = "30",

pages = "6262--6269",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Tungsten(VI) N-heterocyclic carbene complexes: Synthetic, structural, and computational study

AU - Dodds, Christopher A.

AU - Spicer, Mark D.

AU - Tuttle, Tell

PY - 2011/11/28

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.

KW - adducts

KW - carbene compounds

KW - ligands

KW - metals

KW - molecular structure

U2 - 10.1021/om200838f

DO - 10.1021/om200838f

M3 - Article

AN - SCOPUS:81755168919

SN - 0276-7333

VL - 30

SP - 6262

EP - 6269

JO - Organometallics

JF - Organometallics

IS - 22

ER -

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

Abstract

Keywords

ASJC Scopus subject areas

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