Damian Pleschka1, Marcus Layh1, Friedhelm Rogel1, Werner Uhl2. 1. Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 30, 48149 Münster, Germany. 2. Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 30, 48149 Münster, Germany uhlw@uni-muenster.de.
Abstract
Reaction of Mes2P─C≡C─Ph (Mes = mesityl) with dineopentylaluminium hydride afforded by hydroalumination a geminal Al/P-based frustrated Lewis pair (FLP; 4). Its steric shielding is relatively low, and its reactivity in various secondary reactions is less hindered by steric repulsion than observed for related compounds having bulkier groups attached to aluminium. FLP 4 yielded adducts with Me3C─NCO or benzaldehyde via the formation of Al-O and P-C bonds. Trimethylsilyl azide reacted with 4 under surprisingly mild conditions to afford a nitrene complex by spontaneous N2 elimination below room temperature. A carbodiimide molecule was coordinated via one of the C=N bonds to form a five-membered AlCPNC heterocycle with an intact C=N bond in an exocyclic position. A very large molecule was obtained by the reaction of two equivalents of 4 with a bifunctional methylene-bridged phenylene isocyanate precursor.This article is part of the themed issue 'Frustrated Lewis pair chemistry'.
Reaction of n>an class="Chemical">Mes2P─C≡C─Ph (Mes = mesityl) with dineopentylaluminium hydride afforded by hydroalumination a geminalAl/P-based frustrated Lewis pair (FLP; 4). Its steric shielding is relatively low, and its reactivity in various secondary reactions is less hindered by steric repulsion than observed for related compounds having bulkier groups attached to aluminium. FLP 4 yielded adducts with Me3C─NCO or benzaldehyde via the formation of Al-O and P-C bonds. Trimethylsilyl azide reacted with 4 under surprisingly mild conditions to afford a nitrenecomplex by spontaneous N2 elimination below room temperature. A carbodiimide molecule was coordinated via one of the C=N bonds to form a five-membered AlCPNC heterocycle with an intact C=N bond in an exocyclic position. A very large molecule was obtained by the reaction of two equivalents of 4 with a bifunctionalmethylene-bridged phenylene isocyanate precursor.This article is part of the themed issue 'Frustrated Lewis pair chemistry'.