The structures and energies for the addition of free radicals R . (R = H, C
H3, OH, F, SiH3, Cl) to CH2=C=O to give the radicals RCH2C over dot =O, C o
ver dot H-2(C=O)R, CH2=C over dot OR have been calculated by ab initio and
B3LYP-DFT methods, and the latter method gives good agreement with availabl
e experimental energies. Product radicals C over dot H2C(=O)R for groups R
which possess electron lone pairs are stabilized and have predominant spin
density on carbon, and this is attributed to conjugation of the carbonyl gr
oup in the product with substituents OH, F, and Cl at the alpha-position. A
dditions of H and SiH3 have lower barriers to form the more stable product
RCH2C over dot =O, which for the latter is favored due to hyperconjugative
stabilization by the beta-SiH3. For CH3 attack at both carbons is competiti
ve, while for OH, F, and Cl, the barriers are low for attack at either carb
on, although attack at C-alpha gives much more stable products. Initial com
plexes between ketene and the CH3, OH, SiH3, and Cl radicals are detected,
and for Cl using B3LYP this species has the structure of a pi-complex with
the C=C double bond that is stabilized by 16.2 kcal/mol relative to the rea
ctants and forms C over dot H2C(=O)Cl with a barrier of 2.8 kcal/mol. For F
no barriers for addition to either carbon were found, but for B3LYP there
is a barrier of 27.6 kcal/mol for conversion of FCH2C over dot =O to C over
dot H2C(=O)F, which is more stable by 19.1 kcal/mol. The corresponding rea
rrangement of ClCH2C over dot =O has a barrier of 4.6 kcal/mol, and the pre
dicted preference for initial attack at C-beta to give the less stable prod
uct agrees with experiment.