Synthesis of 1-Stannacyclopent-3-enes and Their Pyrolysis to Stannylenes

Autor:	Peter P. Gaspar, John A. Soderquist, Mrinmoy Nag, Clemens Reiche, Dong Zhou
Rok vydání:	2009
Předmět:	Diene Magnesium Organic Chemistry chemistry.chemical_element Photochemistry Medicinal chemistry Oligomer Dissociation (chemistry) Adduct Inorganic Chemistry chemistry.chemical_compound chemistry Physical and Theoretical Chemistry Pyrolysis
Zdroj:	Organometallics. 28:2595-2608
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om800541f
Popis:	1,1-Diorgano-1-stannacyclopent-3-enes have been synthesized by condensation in THF of magnesium complexes of 1,3-dienes and dichlorodiorganostannanes. 1,1-Dimethyl-, 1,1-di-n-butyl-, 1,1-di-tert-butyl-, and 1,1-diphenyl-1-stannacyclopent-3-enes and 1,1,3,4-tetramethyl-, 1,1-di-tert-butyl-3,4-dimethyl-, and 3,4-dimethyl-1,1-diphenyl-1-stannacyclopent-3-enes were prepared. Kinetic studies of the pyrolysis at temperatures as low as 75 °C of several of these stannacyclopent-3-enes resulted in their first-order disappearance, consistent with a unimolecular dissociation to the corresponding stannylene and diene. Activation parameters are reported. Trapping of dimethylstannylene by dienes was overwhelmed by oligomerization of Me2Sn:, but for t-Bu2Sn: a high yield of diene adduct was obtained. The dimethylstannylene oligomer(s) functioned as stannylenoids and were responsible for several reactions previously attributed to free Me2Sn:. cyclo-(t-Bu2Sn)4 may also function as a stannylenoid.
Databáze:	OpenAIRE
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