biostudies-literatureTownsend EMNational Institute of General Medical SciencesNIGMS NIH HHS5334-5341https://www.ebi.ac.uk/biostudies/studies/S-EPMC4195517biostudies-literatureUnknown33(19)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-Ph₄C₆H (STPP) and S-2,6-(mesityl)₂C₆H₃ (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 <i>Z</i>-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.OrganometallicsSynthesis of Molybdenum and Tungsten Alkylidene Complexes That Contain Sterically Demanding Arenethiolate Ligands.PMC4195517R01 GM059426GM-59426Muller PSchrock RRTownsend EMHoveyda AHHyvl JForrest WPfalseSynthesis of Molybdenum and Tungsten Alkylidene Complexes That Contain Sterically Demanding Arenethiolate Ligands.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-Ph₄C₆H (STPP) and S-2,6-(mesityl)₂C₆H₃ (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 <i>Z</i>-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.2014-01-01T00:00:00Z2014 Oct2025-04-26T20:02:18.106Z2019-03-27T01:37:30ZS-EPMC41955172532826710.1021/om500655n