[Ru(NHC)(P-P)(CO)HF] (NHC=N-heterocyclic carbene; P-P=xantphos, dppf) complexes: Efforts to prepare new hydrodefluorination catalysts

Louise M Guard, Araminta E W Ledger, Steven P Reade, Charles E Ellul, Mary F Mahon, Michael K Whittlesey

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Abstract

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 Et3N3HF. 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.
LanguageEnglish
Pages780-786
Number of pages7
JournalJournal of Organometallic Chemistry
Volume696
Issue number3
DOIs
StatusPublished - Feb 2011

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carbenes
Carbon Monoxide
Hydrides
catalysts
Catalysts
Fluorocarbons
Ruthenium
Isomers
Ligands
Heating
Fluorides
hydrides
fluorides
carbene
xantphos
dihydrides
fluorocarbons
ruthenium
isomers
ligands

Keywords

  • C-H activation
  • fluoride ligands
  • N-heterocyclic carbenes
  • ruthenium

Cite this

[Ru(NHC)(P-P)(CO)HF] (NHC=N-heterocyclic carbene; P-P=xantphos, dppf) complexes: Efforts to prepare new hydrodefluorination catalysts. / Guard, Louise M; Ledger, Araminta E W; Reade, Steven P; Ellul, Charles E; Mahon, Mary F; Whittlesey, Michael K.

In: Journal of Organometallic Chemistry, Vol. 696, No. 3, 02.2011, p. 780-786.

Research output: Contribution to journalArticle

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abstract = "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 Et3N3HF. 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.",
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AU - Guard, Louise M

AU - Ledger, Araminta E W

AU - Reade, Steven P

AU - Ellul, Charles E

AU - Mahon, Mary F

AU - Whittlesey, Michael K

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N2 - 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 Et3N3HF. 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.

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