Molybdenum and Tungsten Alkylidene and Metallacyclobutane Complexes That Contain a Dianionic Biphenolate Pincer Ligand
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Schrock_Molybdenum with SI.pdf
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Author(s)
Sues, Peter V. E.
John, Jeremy M
Schrock, Richard Royce
Mueller, Peter
Date Issued
February 2016
Journal
Organometallics
Publisher
American Chemical Society (ACS)
Citation
Sues, Peter E.; John, Jeremy M.; Schrock, Richard R. and Müller, Peter. “Molybdenum and Tungsten Alkylidene and Metallacyclobutane Complexes That Contain a Dianionic Biphenolate Pincer Ligand.” Organometallics 35, no. 5 (March 2016): 758–761. © 2016 American Chemical Society
Version
Author's final manuscript
Abstract
Molybdenum imido alkylidene and tungsten oxo alkylidene complexes that contain a tridentate “pincer” [ONO]²⁻ ligand have been prepared and treated with ethylene to give unsubstituted metallacyclobutane complexes that have a 16e count. Both Mo and W metallacyclobutane complexes exchange C₂D₄ into the metallacyclobutane ring at 22 °C at a rate that is first order in metal and zero order in C₂D₄. These metallacycles lose ethylene at least 10⁴–10⁵ times slower than reported 14e unsubstituted Mo and W metallacyclobutane complexes that have been explored in the literature that have a TBP geometry with the metallacyclobutane ring bound in the equatorial positions. Our studies suggest that breaking up the metallacyclobutane ring in these 16e d⁰ Mo or W complexes is slow because a 14e TBP metallacyclobutane complex cannot be accessed readily.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/acs.organomet.5b00976
