Revisiting the holo- and hemidirected structural transition within the [Pb(CO)n]2+ model series using...

Area of Science:

• Computational chemistry
• Inorganic chemistry
• Materials science

Background:

• Lead carbonyl complexes ([Pb(CO)n](2+)) exhibit diverse structural motifs.
• Static approaches predict hemidirected and holodirected geometries based on ligand count (n).

Purpose of the Study:

• To investigate the influence of thermal effects on the structural dynamics of [Pb(CO)n](2+) complexes.
• To analyze the flexibility and distortions of hemidirected and holodirected structures under simulated thermal conditions.

Main Methods:

• First-principles molecular dynamic simulations were employed.
• Geometrical and topological analyses were used to characterize structural features and distortions.

Main Results:

• All simulated [Pb(CO)n](2+) complexes displayed significant structural flexibility.
• Hemidirected distortions were clearly identified and characterized.
• The octacarbonyl complex ([Pb(CO)8](2+)) showed decoordination of a carbonyl ligand at 300 K.

Conclusions:

• Thermal motion plays a crucial role in the structural behavior of lead carbonyl complexes.
• Dynamic simulations provide insights into the flexibility and potential instability of these complexes, complementing static predictions.