Mechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis
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Mechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangeme.pdf
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ArticleKAUST Department
Chemical Science ProgramKAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2015-06-30Online Publication Date
2015-06-30Print Publication Date
2015-07-13Permanent link to this record
http://hdl.handle.net/10754/575254
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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.Citation
Mechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis 2015, 34 (13):3107 OrganometallicsPublisher
American Chemical Society (ACS)Journal
OrganometallicsAdditional Links
http://pubs.acs.org/doi/abs/10.1021/om501246qae974a485f413a2113503eed53cd6c53
10.1021/om501246q