TY - JOUR
T1 - Synthesis of 1-stannacyclopent-3-enes and their pyrolysis to stannylenes
AU - Zhou, Dong
AU - Reiche, Clemens
AU - Nag, Mrinmoy
AU - Soderquist, John A.
AU - Gaspar, Petet P.
PY - 2009/4/27
Y1 - 2009/4/27
N2 - 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 Me 2Sn:, but for τ-Bu 2Sn: 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 Me 2Sn:. cydo-(τ-Bu 2Sn)4 may also function as a stannylenoid.
AB - 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 Me 2Sn:, but for τ-Bu 2Sn: 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 Me 2Sn:. cydo-(τ-Bu 2Sn)4 may also function as a stannylenoid.
UR - http://www.scopus.com/inward/record.url?scp=65749110918&partnerID=8YFLogxK
U2 - 10.1021/om800541f
DO - 10.1021/om800541f
M3 - Article
AN - SCOPUS:65749110918
VL - 28
SP - 2595
EP - 2608
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 8
ER -