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Abstract
The six-membered N-heterocyclic carbene 1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene (6-Mes) reacts with Ru(PPh3)(3)(CO)HF to afford Ru(6-Mes)(PPh3)(CO)HF (1), which is converted to the five-coordinate C-H activated carbene complex Ru(6-Mes)'(PPh3)(CO)H (2) upon treatment with Et3SiH. The hydride chloride precursor Ru(PPh3)(3)(CO)HCl affords a mixture of products with 6-Mes, but reacts cleanly with 1,3-bis(isopropyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene (6-Pr-i) to give the six-coordinate activated complex Ru(6-Pr-i)'(PPh3)(2)(CO)H (3a), in which the hydride is trans to the methylene arm of the activated NHC. This complex isomerizes in solution with Delta H double dagger and AS double dagger values of 98.2 +/- 4.6 kJ mol(-1) and 15.5 +/- 14.5 J mol(-1) K-1. The major product from the isomerization, 3b, in which the hydride ligand is trans to carbene, can be made directly by reaction of 6-'Pr with Ru(PPh3)(3)(CO)H-2.
Original language | English |
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Pages (from-to) | 991-997 |
Number of pages | 7 |
Journal | Organometallics |
Volume | 29 |
Issue number | 4 |
DOIs | |
Publication status | Published - 26 Jan 2010 |
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Dive into the research topics of 'Ring-expanded n-heterocyclic carbene complexes of ruthenium'. Together they form a unique fingerprint.Projects
- 2 Finished
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A COMBINED EXPERIMENTAL AND COMPUTATIONAL STUDY OF BOND ACTI VATION REACTIONS IN RUTHENIUM N-HETEROCYCLIC CARBENE COMPLEX
Whittlesey, M. (PI)
Engineering and Physical Sciences Research Council
3/03/08 → 2/03/11
Project: Research council
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500 MHZ NMR SPECTROMETER TO SUPPORT ORGANIC, BIO-ORGANIC AND INORGANIC CHEMISTRY
Whittlesey, M. (PI), Danson, M. (CoI), Frost, C. (CoI), Kohn, R. (CoI), Lowe, J. (CoI), Weller, A. (CoI) & Williams, J. (CoI)
Engineering and Physical Sciences Research Council
12/06/06 → 11/06/09
Project: Research council