This study addresses the often-overlooked chemistry of germanium compared to the extensively researched carbon and silicon. Using advanced DFT methods, we investigated the thermal decomposition of germolane (germacyclopentane). The suggested mechanisms include a 1,2-H shift and 1,1-H2 elimination to form a pentacyclic germylene (1λ2-germolane). The other pathway involves a stepwise [3 + 2] cycloreversion to form a diradical followed by ethene and germirane. Under M062X/def2-TZVP level of theory, the activation barriers in terms of Gibbs energy (ΔG‡298) for the 1,2-H shift and 1,1-H2 elimination pathways were 240.9 and 236.3 kJ/mol, respectively. The reaction energies (ΔG°298) for the initiative steps in the 1,2-H shift and 1,1-H2 elimination mechanisms were 102.9 and 96.2 kJ/mol, indicating a thermodynamic and kinetic competition between the two routes. Temperature dependence analysis from 300 to 1200 K reveals that the 1,1-H2 elimination dominates at higher temperatures and is expected to become spontaneous above 1000 K.

Title

Journal of Coordination Chemistry

Publisher

Taylor and Francis

Publisher Country

United Kingdom

Indexing

Scopus

Impact Factor

2.2

Publication Type

Both (Printed and Online)

Volume

3

Year

2024

Pages

13