Cationic beryllium-group 13 heterobimetallic dimetallocenes with a donor-acceptor bond
Fathima Thanha Thazhe Namboorikandy1, Pattiyil Parameswaran1
1Department of Chemistry, National Institute of Technology Calicut, Kozhikode, Kerala, 673601, India. param@nitc.ac.in.
Dalton Transactions (Cambridge, England : 2003)
|December 5, 2025
Summary
This study analyzes heterobimetallic dimetallocenes, revealing a Be-M sigma bond formed by electron donation. Bond strength decreases down Group 13, but covalent character increases, impacting electronic structure.
Area of Science:
- Computational Chemistry
- Organometallic Chemistry
- Inorganic Chemistry
Background:
- Heterobimetallic dimetallocenes featuring beryllium and Group 13 elements are novel compounds.
- Understanding their electronic structure and bonding is crucial for predicting chemical properties.
Purpose of the Study:
- To perform a comprehensive geometrical and bonding analysis of [Cp-Be-M-Cp]+ dimetallocenes.
- To investigate the nature of the Be-M bond across Group 13 elements (B, Al, Ga, In, Tl).
Main Methods:
- Geometry optimization using Density Functional Theory (DFT).
- Molecular Orbital (MO) and Natural Bond Orbital (NBO) analyses.
- Natural Population Analysis (NPA) and Energy Decomposition Analysis with Natural Orbitals for Chemical Valence (EDA-NOCV).
Main Results:
- A collinear geometry was observed, except for the Tl complex.
- A Be-M sigma bond was identified, characterized by a donor-acceptor interaction (Cp-Be+ ← M-Cp).
- Be-M bond strength decreases down Group 13, while the percentage of covalent interaction increases.
Conclusions:
- The Be-M bond exhibits significant charge polarization and a donor-acceptor character.
- Electronic properties are tunable across Group 13 elements, with increasing covalent character down the group.
- These findings provide insights into bonding in novel heterobimetallic systems.
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