Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52056, Aachen, Germany.
WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL, UK.
Chemistry. 2018 Jul 11;24(39):9940-9948. doi: 10.1002/chem.201801541. Epub 2018 Jun 13.
A series of heteroleptic monoamido-monohydrido-dialkylaluminate complexes of general formula [iBu AlTMPHLi⋅donor] were synthesized and characterised in solution and in the solid state. Applying these complexes in catalytic hydroboration reactions with representative aldehydes and ketones reveals that all are competent, however a definite donor substituent effect is discernible. The bifunctional nature of the complexes is also probed by assessing their performance in metallation of a triazole and phenylacetylene and addition across pyrazine. These results lead to an example of phenylacetylene hydroboration, which likely proceeds via deprotonation, rather than insertion as observed with the aldehydes and ketones. Collectively, the results emphasise that reactivity is strongly influenced by both the mixed-metal constitution and mixed-ligand constitution of the new aluminates.
一系列通式为 [iBuAlTMPHLi⋅donor] 的异核单核单氢二烷基铝酸盐配合物被合成并在溶液中和固态下进行了表征。将这些配合物应用于具有代表性的醛和酮的催化硼氢化反应中，结果表明所有配合物都具有催化活性，但可以明显看出一定的供体取代基效应。通过评估它们在三唑和苯乙炔的金属化以及吡嗪加成反应中的性能，也探究了这些配合物的双功能性质。这些结果导致了一个苯乙炔硼氢化的例子，其可能通过去质子化而不是与醛和酮观察到的插入反应进行。总的来说，这些结果强调了反应性强烈受到新型铝酸盐的混合金属组成和混合配体组成的影响。
