This Account summarizes research work on the structural aspects and functio
nal features encountered in all major branches of the Gif family of hydroca
rbon-oxidizing reagents. Despite assertions by the inventor of Gif chemistr
y, D. H. R. Barton, to the effect that nonradical pathways could better exp
lain the behavior of Gif systems, detailed experimental investigations prov
ide compelling evidence to support the preponderance of oxygen- and carbon-
centered radical chemistry.