1st Row Transition Metal Aluminylene Complexes: Preparation, Properties and Bonding Analysis

DOI: 10.14469/hpc/8012 Metadata

Created: 2021-03-22 14:46

Last modified: 2021-03-23 17:54

Author: Richard Yuze Kong

License: Creative Commons: Public Domain Dedication 1.0

Funding: (none given)


The synthesis and spectroscopic characterisation of eight new first-row transition metal (M = Cr, Mn, Fe, Co, Cu) aluminylene complexes is reported. DFT and ab initio calculations have been used to provide detailed insight into the metal–metal bond. The σ-donation and π-backdonation properties of the aluminylene ligand are evaluated via NBO and ETS-NOCV calculations. These calculations reveal that these ligands are strong σ-donors but also competent π-acceptors. These properties are not fixed but vary in response to the nature of the transition metal centre, suggesting that aluminylene fragments can modulate their bonding to accommodate both electron-rich and electron-poor transition metals. Ab initio DLPNO-CCSD(T) calculations show that dispersion plays an important role in stabilising these complexes. Both short-range and long-range dispersion interactions are identified. These results will inform the design of next-generation catalysts for small-molecule and inert-bond activation.


10.14469/hpc/8013 NMR Data
10.14469/hpc/8014 IR Data
10.14469/hpc/8015 Coordinates