Reactions of a Highly Crowded Cyclic Stannylene with Iodoalkanes, Enones, and Dienes. Inhibition of Nucleophilic Substitution at Tin(IV) Centers

作者：Ashrafolmolouk Asadi, Colin Eaborn, Michael S. Hill, Peter B. Hitchcock, Margaret M. Meehan, J. David Smith · 发表于：Organometallics · 年份：2002 · DOI：10.1021/om020106y · 被引用次数：37 · 研究领域：Organometallic Complex Synthesis and Catalysis、Synthesis and characterization of novel inorganic/organometallic compounds、Coordination Chemistry and Organometallics

The cyclic stannylene ( 2; RR = C(SiMe 3 ) 2 SiMe 2 CH 2 CH 2 Me 2 Si(Me 3 Si) 2 C) reacted with alkyl iodides R‘I (R‘ = Et, i Pr) to give the Sn IV compounds ( 6b, c ), which were converted by treatment with silver trifluoroacetate into ( 7b, c ). Reactions of the stannylene 2 with appropriate enones or diones yielded the products ( 10 ), ( 11 ), ( 12 ), and ( 13 ) (OC 14 H 8 O = 9,10-phenanthrenediolato). The crystal structures of 6b, 7b, c, and 10 − 13 have been determined. Treatment of 2 with water, alcohols, or phenol led to ring opening. There is evidence from ESR spectroscopy that the oxidative additions of diones involve radical intermediates. The compound ( 6a ) reacted with ICl to give the chloride ( 15 ), but, in contrast to the previously described crowded trialkyltin halides (Me 3 Si) 3 CSnMe 2 X (X = Cl, I), neither 6a nor 15 reacted with nucleophilic reagents.