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Issue 46, 2015
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Nitrenium ions and trivalent boron ligands as analogues of N-heterocyclic carbenes in olefin metathesis: a computational study

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Abstract

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

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

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Publication details

The article was received on 04 Sep 2015, accepted on 19 Oct 2015 and first published on 20 Oct 2015


Article type: Paper
DOI: 10.1039/C5DT03446A
Author version available: Download Author version (PDF)
Citation: Dalton Trans., 2015,44, 20021-20026
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    Nitrenium ions and trivalent boron ligands as analogues of N-heterocyclic carbenes in olefin metathesis: a computational study

    A. Pazio, K. Woźniak, K. Grela and B. Trzaskowski, Dalton Trans., 2015, 44, 20021
    DOI: 10.1039/C5DT03446A

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