Degree of vinylidene character of α-heteroatom-substituted vinylmagnesium chlorides: a DFT study to discern the role of the halogen atom in magnesium alkylidene carbenoid chemistry

Autor:	Tsutomu Kimura, Tsuyoshi Satoh
Rok vydání:	2013
Předmět:	Magnesium Organic Chemistry Heteroatom chemistry.chemical_element Sulfoxide Antibonding molecular orbital Photochemistry Biochemistry Medicinal chemistry chemistry.chemical_compound chemistry Drug Discovery Atom Halogen Molecular orbital Carbenoid
Zdroj:	Tetrahedron. 69:6371-6374
ISSN:	0040-4020
DOI:	10.1016/j.tet.2013.05.108
Popis:	DFT calculations were performed on a series of α-heteroatom-substituted vinylmagnesium chlorides, CH 2 CXMgCl·2(OMe 2 ) (X=NMe 2 , OMe, F, SMe, Cl, SeMe, and Br), at the B3LYP/6-311++G(d,p) level to elucidate the degree of vinylidene character of such species. α-Halo-substituted vinylmagnesium chlorides were found to have considerable vinylidene character. A donor–acceptor interaction between the C–Mg bonding orbital and the C–X antibonding orbital was responsible for the vinylidene character of α-heteroatom-substituted vinylmagnesium chlorides. A sulfoxide/magnesium exchange reaction of 1-halovinyl phenyl sulfoxides with i -PrMgCl was more exothermic than the exchange reaction of phenyl vinyl sulfoxide with i -PrMgCl by 12.8–13.9 kcal/mol.
Databáze:	OpenAIRE
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