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Issue 11, 2019
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Monomeric Cp3tAl(i): synthesis, reactivity, and the concept of valence isomerism

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Abstract

With the isolation of Cp3tAl (1), the first monomeric Cp-based Al(I) species could be realized in a pure form via a three-step reaction sequence (salt elimination/adduct formation/adduct cleavage) starting from readily available AlBr3. Due to its monomeric structure, reactions involving 1 were found to proceed more selectively, faster, and under milder conditions than for tetrameric (Cp*Al)4. Thus, 1 readily formed simple Lewis acid–base adducts with tBuAlCl2 (6) and AlBr3 (7), reactions that before have always been interfered with by the presence of aluminum halide bonds. In addition, the 2 : 1 reaction of 1 with AlBr3 enabled the realization of the very rare trialuminum adduct species 8. 1 also reacted rapidly with N2O and PhN3 at room temperature to afford Al3O3 and Al2N2 heterocycles 9 and 10, respectively. With the structural characterization of products 4 and 5, the reaction of monovalent 1 with Cp3tAlBr2 (2) provided the first experimental evidence for the concept of valence isomerism between dialanes and their Al(I)/Al(III) Lewis adducts.

Graphical abstract: Monomeric Cp3tAl(i): synthesis, reactivity, and the concept of valence isomerism

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Article information


Submitted
20 Nov 2018
Accepted
12 Jan 2019
First published
14 Jan 2019

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2019,10, 3421-3428
Article type
Edge Article

Monomeric Cp3tAl(I): synthesis, reactivity, and the concept of valence isomerism

A. Hofmann, T. Tröster, T. Kupfer and H. Braunschweig, Chem. Sci., 2019, 10, 3421 DOI: 10.1039/C8SC05175E

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