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Conformational analysis of olefin-carbene ruthenium metathesis catalysts

Benitez, Diego and Tkatchouk, Ekaterina and Goddard, William A., III (2009) Conformational analysis of olefin-carbene ruthenium metathesis catalysts. Organometallics, 28 (8). pp. 2643-2645. ISSN 0276-7333.

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We settle a long-standing disagreement of DFT with experiment (both solution and gas phase) for the phosphine dissociation process in Grubbs metathesis catalysis. Our findings with the M06 functional provide further support to gas-phase experimental work, concluding that for the ring-closing metathesis of norbornene, the resting state is the alkylidene−olefin complex and the rate-determining step is the loss of norbornene as a ligand and generation of the 14-electron activated species. Comparing to recent solution NMR data on olefin−carbene Ru complexes relevant to olefin metathesis, we find that the M06 density functional leads to accurate predictions for the stability of conformers, ~0.5 kcal/mol better than is found by B3LYP. Using this methodology, we suggest that Piers and co-workers observed the cis-dichloro “down” isomer exclusively following the ring opening of acenaphthalene.

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Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2009 American Chemical Society. Published In Issue: April 27, 2009; Article ASAP: March 26, 2009; Received: January 18, 2009; Publication Date (Web): March 26, 2009. This research was partially supported by the NSF-NIRT (CTS-0608889) and MARCO-FENA. Facilities were funded by grants from ARO-DURIP and ONR-DURIP. We acknowledge Dr. Ian C. Stewart and Prof. Robert H. Grubbs for helpful discussions.
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Army Research OfficeUNSPECIFIED
Office of Naval ResearchUNSPECIFIED
Issue or Number:8
Record Number:CaltechAUTHORS:20090721-153201335
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:14632
Deposited By: Jason Perez
Deposited On:08 Aug 2009 20:08
Last Modified:26 Nov 2019 11:15

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