Nitrenium ions and trivalent boron ligands as analogues of N-heterocyclic carbenes in olefin metathesis: a computational study

• DOI: 10.1039/c5dt03446a
• Publication Date: 2015-10-20T09:02:18Z
• Authors: A. Pazio; K. Woźniak; K. Grela; B. Trzaskowski
• Keywords: Olefin Metathesis

We used the density functional theory to evaluate suitability of nitrenium ions and trivalent boron ligands as analogues N-heterocyclic carbenes in ruthenium-based metathesis catalysts. demonstrate that these induce only minor structural changes Hoveyda-Grubbs-like precatalysts, but have major impact on precatalyst initiation. Nitrenium ion-modified precatalysts are characterized by a weak Ru-N bond resulting relatively strong Ru-O large free energy barriers for initiation, making them good candidates efficient latent Ru-based On other hand ligand, bearing formal -1 charge, binds strongly ruthenium ion, weakening facilitating its dissociation, promote fast reaction show calculated dissociation Ru-C/N/B may serve an accurate indicator strength rate