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A Neutral "Aluminocene" Sandwich Complex: ?1 - versus ?5 -Coordination Modes of a Pentaarylborole with ECp* (E=Al, Ga; Cp*=C5 Me5 ).

ABSTRACT: The pentaaryl borole (Ph*C)4 BXylF [Ph*=3,5-tBu2 (C6 H3 ); XylF =3,5-(CF3 )2 (C6 H3 )] reacts with low-valent Group?13 precursors AlCp* and GaCp* by two divergent routes. In the case of [AlCp*]4 , the borole reacts as an oxidising agent and accepts two electrons. Structural, spectroscopic, and computational analysis of the resulting unprecedented neutral ?5 -Cp*,?5 -[(Ph*C)4 BXylF ] complex of AlIII revealed a strong, ionic bonding interaction. The formation of the heteroleptic borole-cyclopentadienyl "aluminocene" leads to significant changes in the 13 C?NMR chemical shifts within the borole unit. In the case of the less-reductive GaCp*, borole (Ph*C)4 BXylF reacts as a Lewis acid to form a dynamic adduct with a dative 2-center-2-electron Ga-B bond. The Lewis adduct was also studied structurally, spectroscopically, and computationally.

SUBMITTER: Sindlinger CP 

PROVIDER: S-EPMC6856865 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

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A Neutral "Aluminocene" Sandwich Complex: η<sup>1</sup> - versus η<sup>5</sup> -Coordination Modes of a Pentaarylborole with ECp* (E=Al, Ga; Cp*=C<sub>5</sub> Me<sub>5</sub> ).

Sindlinger Christian P CP   Ruth Paul Niklas PN  

Angewandte Chemie (International ed. in English) 20190910 42

The pentaaryl borole (Ph*C)<sub>4</sub> BXyl<sup>F</sup> [Ph*=3,5-tBu<sub>2</sub> (C<sub>6</sub> H<sub>3</sub> ); Xyl<sup>F</sup> =3,5-(CF<sub>3</sub> )<sub>2</sub> (C<sub>6</sub> H<sub>3</sub> )] reacts with low-valent Group 13 precursors AlCp* and GaCp* by two divergent routes. In the case of [AlCp*]<sub>4</sub> , the borole reacts as an oxidising agent and accepts two electrons. Structural, spectroscopic, and computational analysis of the resulting unprecedented neutral η<sup>5</sup> -Cp*,η<s  ...[more]

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