[Rh(cycloolefin)(acac)] complexes as catalysts of polymerization of aryl- and alkylacetylenes: Influence of cycloolefin ligand and reaction conditions

Asymmetric polymerisation of substituted phenylacetylene using chiral Rh(2,5-norbornadiene)(L-proline) catalyst

“…These results clearly indicate that [Rh(nbd)Cl] 2 is more catalytically active than the corresponding [Rh(cod)Cl] 2 catalyst in the polymerisation of DoDHPA. This result is similar to that reported earlier (Trhlíková et al, 2013). On the other hand, DoDHPA was also polymerised by using the chiral Rh(nbd)(L-proline) catalyst without a cocatalyst to afford polymers with M r of 36.2 × 10 4 and 28.5 × 10 4 (Table 1), which is higher than the M r of the polymers obtained by using [Rh(nbd)Cl] 2 / (R)-PEA (Table 1) and [Rh(cod)Cl] 2 /(R)-PEA (Table 1) as the Rh(nbd)(L-proline) is more stable in solvent than the [Rh(cod)Cl] 2 /(R)-PEA and [Rh(nbd)Cl] 2 /(R)-PEA catalytic systems.…”

Transition‐Metal‐Catalyzed Chain‐Growth Polymerization of 1,4‐Diethynylbenzene into Microporous Crosslinked Poly(phenylacetylene)s: the Effect of Reaction Conditions

“…1,4‐Diethynylbenzene was polymerized in the chain‐growth mode with Rh, Mo, and W catalysts (see Table ) with the aim to prepare crosslinked PDEB according to Scheme . All the applied catalysts are known to be highly active in the polymerization of monofunctional arylacetylenes, PhA in particular, into (mostly soluble) linear high‐molecular‐weight poly(arylacetylene)s . Conditions and results of DEB polymerizations are summarized in Table where also the codes of the polymers prepared are given.…”

“…Table contains the results of DEB polymerizations with [Rh(nbd)acac] performed in various solvents (CH 2 Cl 2 , benzene, THF, pentane, and methanol). CH 2 Cl 2 , benzene, and THF are known as good solvents for linear poly(phenylacetylene) (PPhA) and were assumed to solvate well also the chain segments of PDEB networks. Pentane and methanol are nonsolvents of PPhA and thus they were assumed to solvate poorly the PDEB segments.…”

“…No correlation between S BET and X BU values is evident for PDEBs from Table . It is known from the literature that the linear poly(arylacetylene)s prepared with Rh‐based catalysts exhibit high‐ cis ‐configuration regardless of the type of the solvent used in the polymerization. In analogy to this, we assume that the configurational structure of PDEBs from Table has not been influenced by the type of the polymerization solvent.…”

New Hyper‐Crosslinked Partly Conjugated Networks with Tunable Composition by Spontaneous Polymerization of Ethynylpyridines with Bis(bromomethyl)arenes: Synthesis, Spectral Properties, and Activity in CO2 Capture

“…The step‐growth homocoupling and cross‐coupling of diethynylarenes provide poly(arylenebutadiynylene)s and poly(aryleneethynylene)s, respectively . The chain‐growth polymerization of mono‐ or disubstituted acetyl­enes results in substituted polyacetylenes and the polycyclotrimerization of mixtures of diethynylarenes and alkylacetylenes provides polyarylene‐type polymers . In the last half a decade, all of the above synthetic paths have been modified for the preparation of conjugated network‐type polymers.…”