Synthesis of Molybdenum and Tungsten Alkylidene Complexes That Contain Sterically Demanding Arenethiolate Ligands
Name
Schrock_Synthesis of Molybdenum.pdf
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Author(s)
Hoveyda, Amir H.
Townsend, Erik M.
Hyvl, Jakub
Forrest Jr, William P
Schrock, Richard Royce
Mueller, Peter
Date Issued
September 2014
Journal
Organometallics
Publisher
American Chemical Society (ACS)
Citation
Townsend, Erik M. et al. “Synthesis of Molybdenum and Tungsten Alkylidene Complexes That Contain Sterically Demanding Arenethiolate Ligands.” Organometallics 33.19 (2014): 5334–5341. © 2014 American Chemical Society 5
Version
Final published version
Abstract
Imido alkylidene complexes of Mo and W and oxo alkylidene complexes of W that contain thiophenoxide ligands of the type S-2,3,5,6-Ph[subscript 4]C[subscript 6]H (STPP) and S-2,6-(mesityl)[subscript 2]C[subscript 6]H[subscript 3] (SHMT = S-hexamethylterphenyl) have been prepared in order to compare their metathesis activity with that of the analogous phenoxide complexes. All thiolate complexes were significantly slower (up to ∼10× slower) for the metathesis homocoupling of 1-octene or polymerization of 2,3-dicarbomethoxynorbornene, and none of them was Z-selective. The slower rates could be attributed to the greater σ-donating ability of a thiophenoxide versus the analogous phenoxide and consequently a higher electron density at the metal in the thiophenoxide complexes.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/om500655n
