Protonation of Hydrido‐Tetrylenes: H2 Elimination vs. Tetrylium Cation Formation

We describe the reactions of amido‐EII hydride complexes, PhiPDippEH (PhiPDipp={[Ph2PCH2SiiPr2](Dipp)N}−; Dipp=2,6‐iPr2C6H3; E=Ge (5), Sn (6)), towards the oxonium complex [(Et2O)2H][BArF4] (ArF=3,5‐CF3‐C6H3). For 5, formation of the dihydro‐tetrylium complex (i. e. [PhiPDippGeH2][BArF4], (7)) is fa...

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Published in:Zeitschrift für anorganische und allgemeine Chemie (1950) 2022-10, Vol.648 (19), p.n/a
Main Authors: Keil, Philip M., Hadlington, Terrance J.
Format: Article
Language:English
Subjects:
Ammonia
ammonia activation
Cations
Dipping
Germanium
H2-elimination
low-valent
Protonation
single-centre ambiphiles
tetryliumylidenes
Tin
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Hadlington, Terrance J.
description We describe the reactions of amido‐EII hydride complexes, PhiPDippEH (PhiPDipp={[Ph2PCH2SiiPr2](Dipp)N}−; Dipp=2,6‐iPr2C6H3; E=Ge (5), Sn (6)), towards the oxonium complex [(Et2O)2H][BArF4] (ArF=3,5‐CF3‐C6H3). For 5, formation of the dihydro‐tetrylium complex (i. e. [PhiPDippGeH2][BArF4], (7)) is favoured, in contrast to the same reaction for 6 which selectively leads to H2 elimination, furnishing the novel tetryliumylidene [PhiPDippSn][BArF4] (4). The related cationic GeII complex (i. e. [PhiPDippGe][BArF4] (3)) could be accessed via the often utilised chloride ion route with Na[BArF4]. The high Lewis acidity of this species has been demonstrated through the reaction of 3 towards the nitrogen bases, NH3 and 4‐dimethylaminopyridine. In the latter case, a classic donor‐acceptor complex is formed. Conversely, for NH3, the [DippN] fragment of the ligand is intriguingly displaced by [HN], presumably through double proton‐transfer in loss of DippNH2.
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For 5, formation of the dihydro‐tetrylium complex (i. e. [PhiPDippGeH2][BArF4], (7)) is favoured, in contrast to the same reaction for 6 which selectively leads to H2 elimination, furnishing the novel tetryliumylidene [PhiPDippSn][BArF4] (4). The related cationic GeII complex (i. e. [PhiPDippGe][BArF4] (3)) could be accessed via the often utilised chloride ion route with Na[BArF4]. The high Lewis acidity of this species has been demonstrated through the reaction of 3 towards the nitrogen bases, NH3 and 4‐dimethylaminopyridine. In the latter case, a classic donor‐acceptor complex is formed. 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For 5, formation of the dihydro‐tetrylium complex (i. e. [PhiPDippGeH2][BArF4], (7)) is favoured, in contrast to the same reaction for 6 which selectively leads to H2 elimination, furnishing the novel tetryliumylidene [PhiPDippSn][BArF4] (4). The related cationic GeII complex (i. e. [PhiPDippGe][BArF4] (3)) could be accessed via the often utilised chloride ion route with Na[BArF4]. The high Lewis acidity of this species has been demonstrated through the reaction of 3 towards the nitrogen bases, NH3 and 4‐dimethylaminopyridine. In the latter case, a classic donor‐acceptor complex is formed. 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For 5, formation of the dihydro‐tetrylium complex (i. e. [PhiPDippGeH2][BArF4], (7)) is favoured, in contrast to the same reaction for 6 which selectively leads to H2 elimination, furnishing the novel tetryliumylidene [PhiPDippSn][BArF4] (4). The related cationic GeII complex (i. e. [PhiPDippGe][BArF4] (3)) could be accessed via the often utilised chloride ion route with Na[BArF4]. The high Lewis acidity of this species has been demonstrated through the reaction of 3 towards the nitrogen bases, NH3 and 4‐dimethylaminopyridine. In the latter case, a classic donor‐acceptor complex is formed. Conversely, for NH3, the [DippN] fragment of the ligand is intriguingly displaced by [HN], presumably through double proton‐transfer in loss of DippNH2.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/zaac.202200141</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0002-4131-8870</orcidid><oa>free_for_read</oa></addata></record>
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subjects Ammonia
ammonia activation
Cations
Dipping
Germanium
H2-elimination
low-valent
Protonation
single-centre ambiphiles
tetryliumylidenes
Tin
title Protonation of Hydrido‐Tetrylenes: H2 Elimination vs. Tetrylium Cation Formation
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