4 research outputs found
Reactivity of Boryl- and Silyl-Substituted Carbenoids toward Alkynes: Insertion and Cycloaddition Chemistry
Three
modes of reactivity of phenyl-substituted alkynes toward
acyclic tetrelenes are reported, with reaction pathways found to be
dependent not only on the nature of the group 14 element but also
on the supporting ligand set. Systems featuring Sn–B or Ge–B
bonds undergo insertion chemistry, forming borane-appended (vinyl)ÂSn<sup>II</sup> and Ge<sup>II</sup> species. With a bisÂ(amido)Âstannylene,
phenylacetylene acts as a protic acid, generating a Sn<sup>II</sup> acetylide with a unique bridged structure. Reactivity toward a more
strongly reducing Si<sup>II</sup> system is dominated by the possibility
of accessing Si<sup>IV</sup> via [2 + 1] cycloaddition chemistry
Oxidative Bond Formation and Reductive Bond Cleavage at Main Group Metal Centers: Reactivity of Five-Valence-Electron MX<sub>2</sub> Radicals
Monomeric five-valence-electron bisÂ(boryl)
complexes of gallium,
indium, and thallium undergo oxidative M–C bond formation with
2,3-dimethylbutadiene, in a manner consistent with both the redox
properties expected for M<sup>II</sup> species and with metal-centered
radical character. The weaker nature of the M–C bond for the
heavier two elements leads to the observation of reversibility in
M–C bond formation (for indium) and to the isolation of products
resulting from subsequent B–C reductive elimination (for both
indium and thallium)
Oxidative Bond Formation and Reductive Bond Cleavage at Main Group Metal Centers: Reactivity of Five-Valence-Electron MX<sub>2</sub> Radicals
Monomeric five-valence-electron bisÂ(boryl)
complexes of gallium,
indium, and thallium undergo oxidative M–C bond formation with
2,3-dimethylbutadiene, in a manner consistent with both the redox
properties expected for M<sup>II</sup> species and with metal-centered
radical character. The weaker nature of the M–C bond for the
heavier two elements leads to the observation of reversibility in
M–C bond formation (for indium) and to the isolation of products
resulting from subsequent B–C reductive elimination (for both
indium and thallium)
Oxidative Bond Formation and Reductive Bond Cleavage at Main Group Metal Centers: Reactivity of Five-Valence-Electron MX<sub>2</sub> Radicals
Monomeric five-valence-electron bisÂ(boryl)
complexes of gallium,
indium, and thallium undergo oxidative M–C bond formation with
2,3-dimethylbutadiene, in a manner consistent with both the redox
properties expected for M<sup>II</sup> species and with metal-centered
radical character. The weaker nature of the M–C bond for the
heavier two elements leads to the observation of reversibility in
M–C bond formation (for indium) and to the isolation of products
resulting from subsequent B–C reductive elimination (for both
indium and thallium)