Synthesis and Thermolysis of Aluminum Amidinates: A Ligand-Exchange Route for New Mixed-Ligand Systems

A novel ligand-exchange route for the synthesis of amidinate-containing compounds of aluminum is explored.
Syntheses of three new compounds, MeC(NiPr)2AlEt2 (4), EtC(NiPr)2AlMe2 (5), and (Me2NC(NiPr)2)2AlH (6), are
presented. These mixed-ligand compounds are difficult to make in high yields by the more traditional routes of
carbodiimide insertion or salt metathesis. The thermal reactivities of these compounds and their parent homoleptic
compounds [MeC(NiPr)2]3Al (1), [Me2NC(NiPr)2]3Al (2), and [EtC(NiPr)2]3Al (3) are explored in detail and analyzed
with respect to their utility as potential atomic-layer-deposition precursors for aluminum-containing films. The major
mechanism of thermal decomposition is found to be carbodiimide deinsertion to form aluminum alkyls or amides.
Because of their thermal characteristics, both compounds 3 and 5 hold promise for use as precursors.

本研究探索了一种新型配体交换途径，用于合成含铝亚胺基化合物。本文介绍了三种新的化合物：MeC(NiPr)2AlEt2 (4)、EtC(NiPr)2AlMe2 (5) 和 (Me2NC(NiPr)2)2AlH (6)。这些混合配体化合物通过更传统的羰基二亚胺插入或盐交换法难以在高产率下制备。详细研究了这些化合物及其同核化合物 [MeC(NiPr)2]3Al (1)、[Me2NC(NiPr)2]3Al (2) 和 [EtC(NiPr)2]3Al (3) 的热反应活性，并分析了它们作为铝含量薄膜潜在原子层沉积前驱体的效用。研究发现，热分解的主要机制是羰基二亚胺脱插入形成铝烷基或酰胺。由于它们的独特热性质，化合物 3 和 5 具有作为前驱体的应用前景。