Ring-expanded n-heterocyclic carbene complexes of ruthenium
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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.
|Creators||Armstrong, R., Ecott, C., Mas-Marza, E., Page, M., Mahon, M. F. and Whittlesey, M. K.|
|Departments||Faculty of Science > Chemistry|
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