Synthesis, structure, and reaction chemistry of a cyclic (alkyl)(amino)aluminyl anion

• Main Author: Koshino, Kota
• Other Authors: Rei Kinjo
• Format: Thesis-Doctor of Philosophy
• Language: English
• Published: Nanyang Technological University 2023
• Subjects: Science::Chemistry::Inorganic chemistry
• Online Access: https://hdl.handle.net/10356/165198
• Institution: Nanyang Technological University

The anionic aluminum(I) species, namely aluminyl anion, is a new class of low-valent aluminum species, which features highly reducing nature and nucleophilic character. Since the first example of nucleophilic aluminum(I) species has been reported in 2018, the field has been rapidly developing over the last four years; however, the derivatives are limited to diamino- and dialkyl-substituted species. This thesis focused on the synthesis of a cyclic (alkyl)(amino)aluminyl anion (CAAAl) and the reactivity study. Chapter 1 mainly covered the progress of aluminyl anion chemistry, including the synthesis methodologies and reactivity studies. Chapter 2 described the first isolation of an (alkyl)(amino)-substituted aluminyl anion based on the five-membered ring, and the electronic structure was revealed using DFT calculations. Chapter 3 explored the reactivity of CAAAl toward small molecules, demonstrating a reductive B–B coupling, σ-bond activations, and a fragmentation of white phosphorus to the P1 unit. Chapter 4 presented the first example of a dialane(6) dianion based on the Al2O three-membered ring, namely, dianionic aluminum analog of oxirane, exhibiting extremely high reactivity resulting from the electron-rich and highly strained Al–Al σ-bond.