Magnesium hydrides bearing sterically demanding amidinate ligands: synthesis, reactivity and catalytic application

Abstract

The synthesis and characterisation of a series of magnesium complexes bearing sterically demanding amidinate ligands is reported; this includes magneisum amides (1a and 1b), hydrides (3a and 3b) and alkyl complexes (2b). The solid and solution state behaviour of the complexes has been investigated using single crystal X-ray diffraction and NMR spectroscopy, revealing the magnesium hydrides to exist as dimers in the solid state, dispite the sterically demanding ligand systems and showing a degree of monomeric character in solution. The stoichiometric and catalytic activity of the amidinate complexes were investigated, with the complexes found to efficiently mediate both the hydroamination of N,N′-diisopropylcarbodiimide and the Tishchenko reaction. The metal hydrides are highly reactive towards coordinating substrates, showing a significant increase in catalytic rate compared with more ubiquitous β-diketiminate magnesium hydrides.