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.
| Language | English |
|---|---|
| Pages | 6262–6269 |
| Number of pages | 8 |
| Journal | Organometallics |
| Volume | 30 |
| Issue number | 22 |
| Early online date | 3 Nov 2011 |
| DOIs | |
| Publication status | Published - 28 Nov 2011 |
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Keywords
- carbene complexes
- N-heterocyclic carbene complexes
- organometallics
- synthetic
- structural
- computational study
Cite this
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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 journal › Article
TY - JOUR
T1 - Tungsten(VI) N-heterocyclic carbene complexes
T2 - Organometallics
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 - carbene complexes
KW - N-heterocyclic carbene complexes
KW - organometallics
KW - synthetic
KW - structural
KW - computational study
U2 - 10.1021/om200838f
DO - 10.1021/om200838f
M3 - Article
VL - 30
SP - 6262
EP - 6269
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 22
ER -