NON-RRKM INTRAMOLECULAR ENERGY-TRANSFER FOLLOWING CHLORINE ATOM ADDITION TO SN(CH=CH2)4

The yield of CH2=CH38Cl from thermal 38Cl reactions with Sn(CH=CH2)4 increases from 66 ± 2% at 4300 Torr to 91 ± 4% at 130 Torr total pressure. The data are consistent with addition of 38Cl to the terminal CH2 positions, followed by a competition between collisional stabilization (in excess CClF3 as bath gas) and decomposition by loss of 38Cl with a half-stabilization pressure of 650 ± 150 Torr. Addition to the C2 position is followed by decomposition to CH2=CH38Cl and (CH2=CH)3Sn. The rapid loss of the 38Cl atom from (CH2=CH)3SnCHCH238Cl* comparable to that from CH2CH238Cl* indicates failure of excitation energy to be transmitted beyond the C-Sn-C central bonding, another example of highly non-RRKM behavior. © 1990 American Chemical Society.