Conformations of N-heterocyclic carbene ligands in ruthenium complexes relevant to olefin metathesis.

Journal of the American Chemical Society
Ian C StewartRobert H Grubbs

Abstract

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 (approximately 0.5 kcal mol-1) accuracy than M06 most likely because it underestimates attractive noncovalent interactions.

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Citations

Nov 22, 2011·Journal of the American Chemical Society·Benjamin K KeitzRobert H Grubbs
Oct 6, 2009·Journal of the American Chemical Society·Kung-Pern WangDonald J Wink
Jun 24, 2010·Nature Chemistry·Edwin F van der Eide, Warren E Piers
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Mar 4, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Yannick BorguetLionel Delaude
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Dec 14, 2018·Beilstein Journal of Organic Chemistry·Magdalena JawiczukBartosz Trzaskowski
Jun 22, 2013·Chemistry : a European Journal·Alessandra PerfettoFabia Grisi
Jun 17, 2011·Chemistry : a European Journal·Chiara CostabileFabia Grisi
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May 28, 2011·Chemistry : a European Journal·Francisco Nuñez-ZarurMariona Sodupe
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Apr 22, 2015·The Journal of Organic Chemistry·Benjamin LarocheBastien Nay
Jan 24, 2018·Organic Letters·Akinobu MatsuzawaKazuyuki Sugita

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