Mechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis

Eva Pump, Christian Slugovc, Luigi Cavallo, Albert Poater

Research output: Contribution to journalArticlepeer-review

22 Scopus citations

Abstract

The intramolecular allenylidene RuCl2(PR3)2(C═C═CPh2) to indenylidene RuCl2(PR3)2(Ind) rearrangement that occurs during the synthesis of Ru-based precatalysts for olefin metathesis is presented. In the absence of acid, the ring closure via C–H activation was shown to be unfavored for energy barriers up to 70 kcal/mol. Thus, it turned out to be HCl (or other acid) that plays a crucial role during formation of the indenylidene, as the upper energy barrier decreases to a reasonable 35 kcal/mol. Moreover, we proved computationally that depending on the nature of the phosphine the intramolecular rearrangement is either facilitated (PPh3) or slightly hampered (PCy3), which is in line with experimental results.
Original languageEnglish (US)
Pages (from-to)3107-3111
Number of pages5
JournalOrganometallics
Volume34
Issue number13
DOIs
StatePublished - Jun 30 2015

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