Two types of intramolecular homolytic substitution reactions at group XIV atoms: unusual radical 1,4-Sn shifts from Si to C and carbonylative SHi reaction at Si |
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Authors: | Studer Armido Amrein Stephan Matsubara Hiroshi Schiesser Carl H Doi Takashi Kawamura Tomonori Fukuyama Takahide Ryu Ilhyong |
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Institution: | Fachbereich Chemie, Universit?t Marburg, Hans-Meerwein-Strasse, D-35032 Marburg, Germany. studer@Mailer.Uni-Marburg.de |
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Abstract: | 4-(Trimethylstannyl)diphenylsilyl]butanoyl radical, arising from the corresponding 3-(stannylsilyl)propyl radical and CO, undergoes an SHi reaction at Si with extrusion of trimethyltin radical to give silacyclopentanone. The parent 3-(stannylsilyl)propyl radical was also found to isomerize to (3-stannylpropyl)silyl radical via a 1,4-Sn shift from Si to C with a rate constant of 9.3 x 10(4) s-1 at 80 degrees C. Ab initio and DFT MO calculations support a front-side attack mechanism. |
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