2 research outputs found

    Cooperative Ge–N Bond Activation in Hydrogallation Products of Alkynyl(diethylamino)germanes (Et<sub>2</sub>N)<sub><i>n</i></sub>Ge(CC<sup><i>t</i></sup>Bu)<sub>4–<i>n</i></sub>

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    Treatment of the alkynyl­(diethylamino)­germanes Et<sub>2</sub>NGe­(CC<sup><i>t</i></sup>Bu)<sub>3</sub> (<b>1</b>) and (Et<sub>2</sub>N)<sub>2</sub>Ge­(CC<sup><i>t</i></sup>Bu)<sub>2</sub> (<b>2</b>) with dialkylelement hydrides <sup><i>t</i></sup>Bu<sub>2</sub>MH (M = Al, Ga) afforded in high yields the hydrometalation products (<sup><i>t</i></sup>BuCC)<sub>2</sub>(Et<sub>2</sub>N)­Ge­[C­(M<sup><i>t</i></sup>Bu<sub>2</sub>)C­(H)<sup><i>t</i></sup>Bu] (<b>3</b>), (<sup><i>t</i></sup>BuCC)­(Et<sub>2</sub>N)­Ge­[C­(M<sup><i>t</i></sup>Bu<sub>2</sub>)C­(H)<sup><i>t</i></sup>Bu]<sub>2</sub> (<b>4</b>) and (<sup><i>t</i></sup>BuCC)­(Et<sub>2</sub>N)<sub>2</sub>Ge­[C­(Ga<sup><i>t</i></sup>Bu<sub>2</sub>)C­(H)<sup><i>t</i></sup>Bu] (<b>6</b>). The Lewis acidic aluminum and gallium atoms showed a close contact to the nitrogen atoms of the amino groups attached to germanium, which resulted in relatively long Ge–N bonds and short Al–N or Ga–N distances. The structures of these molecules and the strengths of the interactions were investigated by dispersion-corrected density functional theory. This activation of the Ge–N bonds caused an unprecedented reactivity of compounds <b>4b</b> and <b>6</b>. <b>4b</b> reacted with PhCCH under mild conditions and elimination of HNEt<sub>2</sub> to give the mixed dialkynyl compound (<sup><i>t</i></sup>BuCC)­(PhCC)­Ge­[C­(Ga<sup><i>t</i></sup>Bu<sub>2</sub>)C­(H)<sup><i>t</i></sup>Bu]<sub>2</sub> (<b>5</b>), while facile insertion of RNCX into a Ge–N bond of <b>6</b> led to the formation of the six-membered Ge–C–Ga–X–C–N heterocycles <b>7</b> (R = Ph, Et; X = O, S)

    Cooperative Ge–N Bond Activation in Hydrogallation Products of Alkynyl(diethylamino)germanes (Et<sub>2</sub>N)<sub><i>n</i></sub>Ge(CC<sup><i>t</i></sup>Bu)<sub>4–<i>n</i></sub>

    No full text
    Treatment of the alkynyl­(diethylamino)­germanes Et<sub>2</sub>NGe­(CC<sup><i>t</i></sup>Bu)<sub>3</sub> (<b>1</b>) and (Et<sub>2</sub>N)<sub>2</sub>Ge­(CC<sup><i>t</i></sup>Bu)<sub>2</sub> (<b>2</b>) with dialkylelement hydrides <sup><i>t</i></sup>Bu<sub>2</sub>MH (M = Al, Ga) afforded in high yields the hydrometalation products (<sup><i>t</i></sup>BuCC)<sub>2</sub>(Et<sub>2</sub>N)­Ge­[C­(M<sup><i>t</i></sup>Bu<sub>2</sub>)C­(H)<sup><i>t</i></sup>Bu] (<b>3</b>), (<sup><i>t</i></sup>BuCC)­(Et<sub>2</sub>N)­Ge­[C­(M<sup><i>t</i></sup>Bu<sub>2</sub>)C­(H)<sup><i>t</i></sup>Bu]<sub>2</sub> (<b>4</b>) and (<sup><i>t</i></sup>BuCC)­(Et<sub>2</sub>N)<sub>2</sub>Ge­[C­(Ga<sup><i>t</i></sup>Bu<sub>2</sub>)C­(H)<sup><i>t</i></sup>Bu] (<b>6</b>). The Lewis acidic aluminum and gallium atoms showed a close contact to the nitrogen atoms of the amino groups attached to germanium, which resulted in relatively long Ge–N bonds and short Al–N or Ga–N distances. The structures of these molecules and the strengths of the interactions were investigated by dispersion-corrected density functional theory. This activation of the Ge–N bonds caused an unprecedented reactivity of compounds <b>4b</b> and <b>6</b>. <b>4b</b> reacted with PhCCH under mild conditions and elimination of HNEt<sub>2</sub> to give the mixed dialkynyl compound (<sup><i>t</i></sup>BuCC)­(PhCC)­Ge­[C­(Ga<sup><i>t</i></sup>Bu<sub>2</sub>)C­(H)<sup><i>t</i></sup>Bu]<sub>2</sub> (<b>5</b>), while facile insertion of RNCX into a Ge–N bond of <b>6</b> led to the formation of the six-membered Ge–C–Ga–X–C–N heterocycles <b>7</b> (R = Ph, Et; X = O, S)
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