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

preprint
submitted on 27.03.2021, 11:02 and posted on 29.03.2021, 12:41 by Richard Y Kong, Mark Crimmin
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 likely inform the design of next-generation catalysts based on aluminium metalloligands.

Funding

Imperial College London: President’s PhD Scholarship (RYK). EPSRC (EP/S036628/1).

History

Email Address of Submitting Author

m.crimmin@imperial.ac.uk

Institution

Imperial College London

Country

United Kingdom

ORCID For Submitting Author

0000-0002-9339-9182

Declaration of Conflict of Interest

No conflicts of interest

Version Notes

Version 1.0

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