期刊
ORGANOMETALLICS
卷 30, 期 22, 页码 6262-6269出版社
AMER CHEMICAL SOC
DOI: 10.1021/om200838f
关键词
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资金
- EPSRC
- EPSRC [EP/E036244/1, EP/F031769/1] Funding Source: UKRI
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 sigma-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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