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

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

A.P. thanks the Spanish MINECO for Project CTQ2014-59832-JIN and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)

American Chemical Society (ACS)

Manager: Ministerio de Econom铆a y Competitividad (Espanya)
Author: Pump, Eva
Slugovc, Christian
Cavallo, Luigi
Poater Teixidor, Albert
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
A.P. thanks the Spanish MINECO for Project CTQ2014-59832-JIN and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)
Document access: http://hdl.handle.net/2072/298698
Language: eng
Publisher: American Chemical Society (ACS)
Rights: Tots els drets reservats
Subject: Met脿tesi (Qu铆mica)
Metathesis (Chemistry)
Alquens
Alkenes
Title: Mechanism of the Ru-Allenylidene to Ru-Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis
Type: info:eu-repo/semantics/article
Repository: Recercat

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