The reaction of Me(3)GeC(6)H(5) and Me(3)GeC(6)H(4)Me with Me(2)CH(+), Me(3)C(+), and Me(2)Cl(+) has been studied in the gas phase at pressures spanning from 1 Torr (chemical ionization mass spectrometry) to 1 atm (radiolytic technique). The reactions conform to the general model of electrophilic aromatic substitution reactions, proceeding via sigma-complex intermediates, which show a tendency to isomerize to arenium ions bearing a proton on the germylated carbon. Such 1,2-H shift processes occur in the time scale of 10(-8) s. The fate of the germylated arenium ions is controlled by competing deprotonation and degermylation reactions showing a behavior similar to their silicon analogues. The Me(3)X (X = Si, Ge) groups are seen to show a comparable electronic effect with regard to electrophilic attack at the unsubstituted ring positions of an attached phenyl group. (C) 1997 Elsevier Science B.V.

Gas phase alkylation of phenyltrimethylgermanes / Chiavarino, Barbara; Crestoni, Maria Elisa; Fornarini, Simonetta. - In: JOURNAL OF ORGANOMETALLIC CHEMISTRY. - ISSN 0022-328X. - STAMPA. - 545(1997), pp. 45-51. [10.1016/s0022-328x(97)00315-x]

Gas phase alkylation of phenyltrimethylgermanes

CHIAVARINO, Barbara;CRESTONI, Maria Elisa;FORNARINI, Simonetta
1997

Abstract

The reaction of Me(3)GeC(6)H(5) and Me(3)GeC(6)H(4)Me with Me(2)CH(+), Me(3)C(+), and Me(2)Cl(+) has been studied in the gas phase at pressures spanning from 1 Torr (chemical ionization mass spectrometry) to 1 atm (radiolytic technique). The reactions conform to the general model of electrophilic aromatic substitution reactions, proceeding via sigma-complex intermediates, which show a tendency to isomerize to arenium ions bearing a proton on the germylated carbon. Such 1,2-H shift processes occur in the time scale of 10(-8) s. The fate of the germylated arenium ions is controlled by competing deprotonation and degermylation reactions showing a behavior similar to their silicon analogues. The Me(3)X (X = Si, Ge) groups are seen to show a comparable electronic effect with regard to electrophilic attack at the unsubstituted ring positions of an attached phenyl group. (C) 1997 Elsevier Science B.V.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/242913
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