By contrast to typical high-temperature (100-250 °C) telo-/polymerizations of gaseous fluorinated monomers, carried out in high-pressure metal reactors, the visible light, Mn(2)(CO)(10)-photomediated initiation of vinylidene fluoride (bp = -83 °C) polymerization occurs readily from a variety of alkyl, semifluorinated, and perfluorinated halides at 40 °C, in low-pressure glass tubes and in a variety of solvents, including water and alkyl carbonates. Perfluorinated alkyl iodide initiators also induce a controlled radical polymerization via iodine degenerative transfer (IDT). While IDT proceeds with accumulation of the less reactive P(m)-CF(2)-CH(2)-I vs the P(n)-CH(2)-CF(2)-I chain ends, Mn(2)(CO)(10) enables their subsequent quantitative activation toward the synthesis of well-defined poly(vinylidene fluoride) block copolymers with a variety of other monomers.

IFAB-ulous trifluoromethylation: (CX3COO)2I(III) h (X=F, H) and (CH3COO)3I(V)(C6H4COO) are introduced as CX3·/CX3I precursors for metal-free, visible-light, radical (trifluoro)(iodo)methylations of alkenes, illustrated by their use as photoinitiators for the controlled radical polymerization of vinylidene fluoride with external (I(CF2)6I) and in situ generated (CF3I) iodine chain transfer agents, and for block copolymer synthesis.

The metal and ligand effect of a series of transition metal carbonyls in conjunction with alkyl and perfluoroalkyl halides was investigated in the initiation and control of the visible light, radical photopolymerizations of vinylidene fluoride (VDF) and respectively, in the synthesis of PVDF block copolymers. No polymerization was observed for CpMn­(CO)3, CpCo­(CO)2, Cp2Fe2(CO)4, Cp*2Cr2(CO)4, Mo­(CO)6, Fe­(CO)5, Cr­(CO)6, Co2(CO)8, Co4(CO)12, Fe3(CO)12, Ru3(CO)12, (PPh3)2Ni­(CO)2, Cp2Ti­(CO)2, and Au­(CO)­Cl. A free radical polymerization, and respectively an iodine degenerative transfer, controlled radical polymerization was obtained for Mn2(CO)10 ∼ Re2(CO)10 ≫ Cp2Mo2(CO)6 ≫ Cp2W2(CO)6 with CH3(CH2)5–Br, CH3(CH2)5–I, CH3–I, CCl3–Cl, CCl3–Br, Br–(CF2)6–Br, and respectively with CF3(CF2)3–I and I–(CF2)4,6–I. Furthermore, while Fe­(CO)5, Cp*Cr2(CO)4 and Co4(CO)12 led to ∼ CF2–I bond insertion, Re2(CO)10, Mn2(CO)10, Cp2W2(CO)6, Cp2Mo2(CO)6 and Cp2Fe2(CO)4 provided quantitative radical activation of both PVDF–CH2–CF2–I and PVDF–CF2–CH2–I chain ends, and were employed in the synthesis of well-defined ABA triblock PVDF copolymers with vinyl acetate, tert-butyl acrylate, methyl methacrylate, isoprene, styrene, and acrylonitrile.

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