Pentacoordinate silyl peroxides

IV. SYNTHESIS OF ALCOHOLS VIA HEXA- AND PENTACOORDINATE SILYL PEROXIDES... 

Particle emissions, diesel fuel additive, 624 Partition number, conjugated dienes, 671 Pasteurization, lactoperoxidase, 612, 631, 634 Paterno-Buchi triplet 1,4-diradical, 290-1 PCPO see Bis(pentachlorophenyl) oxalate Pentacoordinate silyl peroxides, 808-10 Pentacosane, thermal oxidation, 685 O -Pentafluorobenzylhydroxyamine, aldehyde determination, 670... 

The rearrangement 12 13 is not straightforward and two alternatives routes have been suggested. One of them involves a 1,3 transfer from silicon to oxygen to give the silyl radical 15 followed by Sui reaction on the peroxide moiety [15]. The other indicated by PM3 calculations is a dioxirane-like three-membered intermediate 16 having a pentacoordinated central silicon followed by a 1,2 silyl migration to afford radical 13 [19]. 

---