GeCl2 cycloaddition reactions to unsaturated organic compounds taking ethylene, buta-1,3-diene, and hexa-1,3,5-triene as examples: a quantum chemical study

• Published in: Russian chemical bulletin 2010-06, Vol.59 (6), p.1099-1109
• Main Authors: Rynin, S. S., Faustov, V. I., Boganov, S. E., Egorov, M. P., Nefedov, O. M.
• Format: Article
• Language: English
• Subjects: Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Full Articles; Inorganic Chemistry; Organic Chemistry
• ISSN: 1066-5285; 1573-9171
• DOI: 10.1007/s11172-010-0211-3

The cycloaddition reactions of dichlorogermylene GeCl 2 to ethylene, buta-1,3-diene, and hexa-1,3,5-triene were studied within the framework of the density functional theory (PBE and B3LYP density functionals) and by the ab initio CBS-QB3 method. The energy characteristics of the reaction of GeCl 2 with ethylene were refined and non-empirical quantum chemical calculations of reaction pathways in the GeCl 2 + buta-1,3-diene and GeCl 2 + hexa-1,3,5-triene systems were carried out for the first time. It was shown that the [2+1] cycloaddition reactions are kinetically hindered and thermodynamically unfavorable, while the [4+1] and [6+1] cycloaddition reactions are characterized by low barriers and result in thermodynamically favorable products. For the [4+1] cycloaddition to buta-1,3-diene and [6+1] cycloaddition to hexa-1,3,5-triene, the most energetically favorable reaction pathways involve a suprafacial and antarafacial approach of reactants, respectively.