Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 131, Issue 5, Pages 1931-1938Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja8078913
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Funding
- NIH [F32GM078734, K99GM084302, 5ROIGM31332]
- NSF [NIRT(CTS-0608889), CHE-0410425]
- Pomona College Chemistry Department
- ARODURIP
- ONR-DURIP
- U.S. Department of Energy
- NSF CRIF:MU award [CHE-0639094]
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The structure of ruthenium-based olefin metathesis catalyst 3 and model pi-complex 5 in solution and in the solid state are reported. The N-tolyl ligands, due to their lower symmetry than the traditional N-mesityl substituents, complicate this analysis, but ultimately provide explanation for the enhanced reactivity of 3 relative to standard catalyst 2. The tilt of the N-tolyl ring provides additional space near the ruthenium center, which is consistent with the enhanced reactivity of 3 toward sterically demanding substrates. Due to this tilt, the more sterically accessible face bears the two methyl substituents of the N-aryl rings. These experimental studies are supported by computational studies of these complexes by DFT. The experimental data provides a means to validate the accuracy of the B3LYP and M06 functionals. B3LYP provides geometries that match X-ray crystal structural data more closely, though it leads to slightly less (similar to 0.5 kcal mol(-1)) accuracy than M06 most likely because it underestimates attractive noncovalent interactions.
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