1600534-78-8

Upstream product

• 1219805-53-4 C₁₀H₁₁⁽²⁾H₆N 
• 1600534-77-7 N-(adamantan-1-yl-2,2,8,8,9,9-d₆)-2-bromoacetamide 
• 88-05-1 2,4,6-trimethylaniline 

Downstream Products

• 1600534-81-3 1-(adamantan-1-yl-2,2,8,8,9,9-d₆)-3-(2,4,6-trimethylphenyl)-4,5-dihydro-1H-imidazol-3-iumchloride 
• 1600534-79-9 C₂₁H₂₆⁽²⁾H₆N₂ 

Relevant academic research and scientific papers

Carboxylate-assisted C(sp3)-H activation in olefin metathesis-relevant ruthenium complexes

The mechanism of C-H activation at metathesis-relevant ruthenium(II) benzylidene complexes was studied both experimentally and computationally. Synthesis of a ruthenium dicarboxylate at a low temperature allowed for direct observation of the C-H activation step, independent of the initial anionic ligand-exchange reactions. A first-order reaction supports an intramolecular concerted metalation-deprotonation mechanism with ? 298K = 22.2 ± 0.1 kcal·mol-1 for the parent N-adamantyl-N-mesityl complex. An experimentally determined ? =-5.2 ± 2.6 eu supports a highly ordered transition state for carboxylate-assisted C(sp3)-H activation. Experimental results, including measurement of a large primary kinetic isotope effect (k H/kD = 8.1 ± 1.7), agree closely with a computed six-membered carboxylate-assisted C-H activation mechanism where the deprotonating carboxylate adopts a pseudo-apical geometry, displacing the aryl ether chelate. The rate of cyclometalation was found to be influenced by both the electronics of the assisting carboxylate and the ruthenium ligand environment.