Click Synthesis and Redox Chemistry of Mono‐ and Heterobimetallic Triazolyl and Triazolium‐Ferrocene and Cobalticinium Complexes

Abstract

Mono-and heterobimetallic triazolylferrocene and cobalticinium complexes and triazolium derivatives were synthesized by click reactions between the ethynylmetallocenes and benzyl azide or (azidomethyl)ferrocene followed by methylation reactions, respectively. Cyclic voltammetry data shed light on the electron-withdrawing character of the 1,2,3-triazolyl and triazolium substituents of the metallo-[a] ISM,

Facile Preparation of Cobaltocenium‐Containing Polyelectrolyte via Click Chemistry and RAFT Polymerization

“…The reduction peak current at −0.84 V is much higher than the oxidation peak current at −0.72 V. The redox potential is similar to early results on side‐chain cobaltocenium‐containing polymers, which show redox peaks around −0.9 and −0.6 V . The change of the reduction potential may attribute to the electron‐withdrawing properties of the 1,2,3‐triazolyl group . The irreversibility may be attributed to the solubility change during the redox process .…”

“…There are reports that different functional groups have been introduced by using such method, in which the ethynyl‐substitution strategy is more interesting and useful. Through facile copper‐catalyzed azide–alkyne cycloaddition (CuAAC) by reacting with azide species, the ethynyl‐substituted cobaltocenium can be further derivatized into suitable monomers. Furthermore, such kind of ethynyl‐substituted cobaltocenium can be also used for efficient postpolymerization modification of azide polymers …”

Highly Electrophilic, Catalytically Active and Redox‐Responsive Cobaltoceniumyl and Ferrocenyl Triazolylidene Coinage Metal Complexes

“…Note that a diferrocenylated triazole, made similarly by cycloaddition of azidoferrocene with ethynylferrocene, is not included, because its synthesis and further chemistry has already recently been published . We also note that only one related example of a heterobimetallic cobaltoceniumyl/ferrocenyl triazole and triazolium containing a methylene‐spacered ferrocenyl substituent has been synthesized and electrochemically investigated, however, no metal complexes have been prepared therefrom.…”

Ring‐Opening Metathesis Polymerization of 18‐e Cobalt(I)‐Containing Norbornene and Application as Heterogeneous Macromolecular Catalyst in Atom Transfer Radical Polymerization

“…It is stable in air for several days and can be stored under N 2 at room temperature longer than 30 d without noticeable change, as monitored by 1 H NMR (Figure S6, Supporting Information). As shown in Figure S9 (Supporting Information), the cyclic voltammetry of polymer 2 in DMF with TBAPF 6 as a supporting electrolyte displays two irreversible oxidation peaks around 1.1 and 1.5 V versus Ag/AgCl electrode, which can be attributed to the oxidation of the center Co(I) . According to thermogravimetric analysis (TGA) (Figure S8, Supporting Information), polymer 2 is stable until 140 °C.…”