Disilametallacycles as a Platform for Stabilizing
M(II) and M(IV) (M = Fe, Ru)
Centers: Synthesis and Characterization of Half-Sandwich Complexes
and Their Application to Catalytic Double Silylation of Alkenes and
Alkynes
- Publication date
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Abstract
A series of group 8 half-sandwich
disilametallacycles, (η<sup>6</sup>-arene)M<sup>II</sup>(Me<sub>2</sub>SiC<sub>6</sub>H<sub>4</sub>SiMe<sub>2</sub>)L and (η<sup>6</sup>-arene)M<sup>IV</sup>(H)<sub>2</sub>(Me<sub>2</sub>SiC<sub>6</sub>H<sub>4</sub>SiMe<sub>2</sub>) (M = Fe, Ru) in the formal
oxidation states of M(II) and M(IV)
were synthesized and characterized. Both the M(II) and the M(IV) oxidation
states were effectively stabilized by the disilametallacycle skeleton,
and facile interconversion between (η<sup>6</sup>-arene)M<sup>II</sup>–dinitrogen, (η<sup>6</sup>-arene)M<sup>II</sup>–carbonyl, and (η<sup>6</sup>-arene)M<sup>IV</sup>–dihydride
complexes bearing a disilaferracycle framework was accomplished. These
M(II) and M(IV) complexes can easily generate coordinatively unsaturated
16e disilametallacycles, (η<sup>6</sup>-arene)M<sup>II</sup>(Me<sub>2</sub>SiC<sub>6</sub>H<sub>4</sub>SiMe<sub>2</sub>), by
dissociation of L or H<sub>2</sub>, and stoichiometric and/or catalytic
double silylation of alkenes and alkynes was realized thorough this
16e intermediate
