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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.

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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.

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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.