A Brief Computational Study of Decamethyldizincocene Formation via Diethylzinc and Decamethylzincocene

Autor:	Yan Alexander Wang, Steven S. Hepperle
Rok vydání:	2008
Předmět:	chemistry.chemical_compound chemistry Activation barrier Radical Ab initio Decamethyldizincocene Density functional theory Physical and Theoretical Chemistry Diethylzinc Photochemistry Dissociation (chemistry) Homolysis
Zdroj:	The Journal of Physical Chemistry A. 112:9619-9622
ISSN:	1520-5215 1089-5639
Popis:	We have used density functional theory and ab initio methods to study different mechanistic possibilities for the formation of decamethyldizincocene from the reaction between decamethylzincocene and diethylzinc. Our results suggest that decamethyldizincocene could form from the combination of two pentamethylcyclopentadienylzinc radicals. More importantly, our data show that homolytic dissociation of decamethylzincocene into pentamethylcyclopentadienylzinc and pentamethylcyclopentadienyl radicals is 6.7 kcal/mol less costly than the analogous dissociation of zincocene. If such an energy difference is coupled with the fact that the activation barrier to form the half-sandwich product pentamethylcyclopentadienylethylzinc is 11.8 kcal/mol more costly than to form cyclopentadienylethylzinc, we can rationalize why dizincocene does not form experimentally.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::1b35dae18a274a33963d6ccf45ac11a4 https://doi.org/10.1021/jp804364j Zobrazit plný text záznamu