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.

العنوان

Journal of Coordination Chemistry

الناشر

Taylor and Francis

بلد الناشر

المملكة المتحدة

Indexing

Scopus

معامل التأثير

2,2

نوع المنشور

Both (Printed and Online)

المجلد

3

السنة

2024

الصفحات

13