کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1322531 | 977213 | 2011 | 7 صفحه PDF | دانلود رایگان |
The ruthenium N-heterocyclic carbene (NHC) hydride fluoride complexes Ru(NHC)(P–P)(CO)HF (NHC = ICy (3), IEt2Me2 (5), P–P = xantphos; NHC = ICy (7), P–P = dppf) have been prepared by treatment of the corresponding dihydride complexes [Ru(NHC)(P–P)(CO)H2] (NHC = ICy (2), IEt2Me2 (4) P–P = xantphos; NHC = ICy (6), P–P = dppf) with Et3N·3HF. In all cases, the hydride fluoride complexes exist in solution as two conformers or isomers. Although 3, 5 and 7 could be converted back to 2, 4 and 6, respectively, by heating with Et3SiH, efforts to generate a catalytic cycle for the hydrodefluorination of aromatic fluorocarbons by subsequent reaction of Ru(NHC)(P–P)(CO)H2 with C6F6 were prevented by the much more favourable cyclometallation of the carbene ligand.
Treatment of [Ru(NHC)(P–P)(CO)H2] (NHC = N-heterocyclic carbene; P–P = xantphos, dppf) with Et3N·3HF affords the corresponding hydride fluoride species [Ru(NHC)(P–P)(CO)HF]. Studies on the interconversion of these two sets of compounds in a cycle for the catalytic hydrodefluorination of aromatic fluorocarbons have been undertaken.Figure optionsDownload as PowerPoint slideResearch highlights
► New ruthenium N-heterocyclic carbene hydride fluoride complexes exist as mixtures of isomers at low temperature.
► These species can be converted to the corresponding dihydride complexes upon treatment with alkysilanes.
► Efforts to establish a catalytic cycle for hydrodefluorination of aromatic fluorocarbons are thwarted by facile intramolecular C–H activation of the NHC ligands.
Journal: Journal of Organometallic Chemistry - Volume 696, Issue 3, 1 February 2011, Pages 780–786