Synthesis, structure and cationic ring-opening polymerization (ROP) of a strained [2]carbathioferrocenophane

Abstract

The synthesis and cationic ring-opening polymerization of a novel [2]carbothiaferrocenophane is reported; the polymerization represents the first cationic ring-opening polymerization of a metal-containing ring.

References

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19. For 3: ¹H NMR (400 MHz, C₆D₆): δ 4.69 (m, 2 H, η-C₅H₄), 4.17 (s, 2 H, CH₂S), 3.64 (m, 2 H, η-C₅H₄), 2.41 (s, 6 H, η-C₅Me₄), 1.65 (s, 6 H, η-C₅Me₄); ¹³C NMR (400 MHz, C₆D₆, room temp.): δ 93.7 (Cp_ipso), 84.7 (η-C₅Me₄), 84.6 (η-C₅H₄), 83.8 (Cp′_ipso), 81.2 (η-C₅Me₄), 71.2 (η-C₅H₄), 42.6 (CH₂S), 12.3 (η-C₅Me₄), 11.2 (η-C₅Me₄); GC–MS (70 eV): m/z(%) 286 (100)[M⁺], 194 (8)[M⁺– 4CH₃– S], 126 (11)[M⁺– 4CH₃– CH₂– S – Fe].
20. A crystal of 3 suitable for X-ray diffraction analysis was obtained from a recrystallization in minimal hexanes at –30 °C.
21. For 4: ¹H NMR (400 MHz, C₆D₆): δ 3.65 (br, m, 6 H, η-C₅H₄, CH₂S), 2.95 (br, s, CH₃OTf), 1.61 (br, s, 12 H η-C₅Me₄).
22. For 4: ¹³C CP MAS NMR (400 MHz, 8 kHz spin rate): δ 83.6–72.1 (br, m, η-C₅Me₄, η-C₅H₄), 35.9 (br, s, CH₂), 10.4 (br, s, C₅Me₄).