Polynorbornenes Containing Ferrocene Derivatives and Alkyne‐bis(tricarbonylcobalt)

Abstract

Coordination of dicobalt hexacarbonyl to the alkyne moiety of norbornene complexes containing either ferrocene or η(6) -chlorobenzene-η(5) -cyclopentadienyliron hexafluorophosphate, gave two unique trimetallic complexes available for ROMP. Polymerization of each monomer using Grubbs second generation catalyst gave organoiron/organocobalt polynorbornenes with weight average molecular weights between 55 300 and 69 000 with PDIs between 1.2 and 1.9. Cyclic voltammetric studies of the monomers and polymers at -40 °C showed a reversible reduction for cationic complexes containing η(6) -benzene-η(5) -cyclopentadienyliron and for the dicobalt hexacarbonyl moieties while, a reversible oxidation for the ferrocene containing complex was observed. Thermal analysis showed that the cobalt carbonyl moiety of the polymers degraded near 130 °C; however, the polymeric backbone was stable up to 350 °C. Scanning electron microscopy (SEM) and SEM-EDS indicated that the polymers possessed a fine globular morphology and that the distribution of iron and cobalt atoms was homogenous on the macro-scale.

Sandwich Complex‐Containing Macromolecules: Property Tunability Through Versatile Synthesis

“…Abd‐El‐Aziz and co‐workers reported Grubbs second‐generation catalyst‐mediated, ROMP of ferrocene and η 6 ‐chlorobenzene‐ η 5 ‐cyclopentadienyliron hexafluorophosphate norbornene monomers . The monomers were synthesized through a multi‐step synthetic method that involves Steglich esterification reaction of the sandwich complex with 2‐butyne‐1,4‐diol and subsequent reaction of the monohydroxyl sandwich complex‐containing product with 5‐carboxyl‐2‐norbornene to give the alkyne‐, sandwich complex‐containing norbornene complex (Schemes and ).…”

“…Ring-opening polymerization is also utilized in the synthesis of macromolecules featuring pendent sandwich complexes. [205][206][207][208] For instance, the living anionic Scheme 35. Radical polymerizations of methyl-substituted cyclobutadiene sandwich complex-containing acrylate.…”

Redox‐Robust Pentamethylferrocene Polymers and Supramolecular Polymers, and Controlled Self‐Assembly of Pentamethylferricenium Polymer‐Embedded Ag, AgI, and Au Nanoparticles

“…[10] Therefore, PMF polymersw ere targeted here by using the ring-opening metathesis polymerization (ROMP) reaction. [11] The ROMPs ynthesis of ferrocene polymers [11][12][13][14] has been known for more than twenty years, although the resulting polymers show modest polydispersities and are often oligomers or polymers with ar elativelys mall number of pendant ferrocenyl units. [11,12] Recent ROMP reactions by using thirdgeneration Grubbs catalyst 1 have provided polymers of low polydispersities, [13] including metallocene polymers.…”

“…However,s low oxidation of 6 50 occurred upon addition of at enfolde xcesso f iodine to 6 50 .When as olution of AgPF 6 in toluenewas injected into aC H 2 Cl 2 /toluene solutiont hat contained polymer 6 50 and 0.15 equivalent of iodine (vs.t he total PMF units) that had been stirred for 2h,t he color changed from light yellow to light brown (12). The UV/Vis spectrum ( Figure 5) of this solution of 12 showsamixture of AgI NPs and Ag NPs, [22] and the core sizes determined by TEM and HRTEM show two populations of NPs of around5and 20 nm.…”

Living ROMP Synthesis and Redox Properties of Triblock Metallocopolymers Containing Side‐Chain Iron and Cobalt Sandwich Complexes

“…[49][50][51][52] This method was used early on by Schrock to synthesize Fc-containing polymers, [53] and Grubbs ruthenium metathesis catalysts have later been largely used for this purpose. [54][55][56][57][58][59][60][61][62][63][64] The advent of the most modern metathesis catalysts, [65][66][67] and in particular the air-and water-stable Grubbs catalyst 1 of 3rd generation, [66,67] has allowed living polymerization systems that are ideal for the synthesis of block copolymers (Figure 1). The resulting late-transition metal sandwich-containing polymers and block copolymers have been the subject of excellent recent reviews, [14,68] but in this series, copolymers containing more than two metalloblocks are rare.…”