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Article Dans Une Revue Organometallics Année : 2021

Catalytic Alkyne and Diyne Metathesis with Mixed Fluoroalkoxy-Siloxy Molybdenum Alkylidyne Complexes

Résumé

The reaction of the molybdenum alkylidyne complex [MesC=Mo{OC(CF3)(3)}(3)] (MoF9, Mes = 2,4,6-trimethylphenyl) with the potassium siloxides KOSi(OtBu)(3) and KOSi(OtBu)(2) (OMes) furnished the mixed fluoroalkoxy-siloxy alkylidyne complexes [MesC Mo{OC(CF3)(3)}(2) {OSi(OtBu)(3)}] (MoSiF9) and [MesC Mo{OC(CF3)(3)}(2) {OSi(OtBu)(2) (OMes)}] (MoSi*F9). A treatment of MoF9, MoSiF9, and MoSi*F9 with an excess of 3-hexyne (EtC CEt) afforded labile metallacyclobutadiene (MCBD) complexes with a (C3Et3)Mo core, which are in equilibrium with the corresponding propylidyne (EtC Mo) complexes in solution. Thermodynamic parameters for these [2 + 2]-cycloaddition/cycloreversion reactions were determined by van't Hoff plots, revealing that the nature of the ancillary siloxide ligand exerts a significant effect on the MCBD stability. An X-ray diffraction analysis of MoSi*F9-MCBD provided one of the first accurate crystal structures of a molybdenacyclobutadiene. MoF9, MoSiF9, and MoSi*F9 proved active catalysts for the metathesis of internal alkynes and diynes, with MoSi*F9 showing unprecendented selectivity in the conversion of sterically encumbered 1,3-pentadiynes into symmetrical 1,3,S-triynes and 2-butyne.
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Dates et versions

hal-03330984 , version 1 (15-09-2021)

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Manuel L. Zier, Sophie Colombel-Rouen, Henrike Ehrhorn, Dirk Bockfeld, Yann Trolez, et al.. Catalytic Alkyne and Diyne Metathesis with Mixed Fluoroalkoxy-Siloxy Molybdenum Alkylidyne Complexes. Organometallics, 2021, 40 (12), pp.2008-2015. ⟨10.1021/acs.organomet.1c00290⟩. ⟨hal-03330984⟩
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