Air-Stable Single-Component Pd-Catalysts for Vinyl-Addition Polymerization of Functionalized Norbornenes
- Evgeniya V. BermeshevaEvgeniya V. BermeshevaA.V. Topchiev Institute of Petrochemical Synthesis, RAS, 29 Leninskiy pr., Moscow 119991, RussiaI.M. Sechenov First Moscow State Medical University, Trubetskaya str., 8, building 2, Moscow 119991, RussiaMore by Evgeniya V. Bermesheva
- ,
- Ekaterina I. MedentsevaEkaterina I. MedentsevaA.V. Topchiev Institute of Petrochemical Synthesis, RAS, 29 Leninskiy pr., Moscow 119991, RussiaMore by Ekaterina I. Medentseva
- ,
- Anna P. KhrychikovaAnna P. KhrychikovaA.V. Topchiev Institute of Petrochemical Synthesis, RAS, 29 Leninskiy pr., Moscow 119991, RussiaD.I. Mendeleyev University of Chemical Technology of Russia, 9 Miusskaya sq., Moscow 125047, RussiaMore by Anna P. Khrychikova
- ,
- Alyona I. WozniakAlyona I. WozniakA.V. Topchiev Institute of Petrochemical Synthesis, RAS, 29 Leninskiy pr., Moscow 119991, RussiaMore by Alyona I. Wozniak
- ,
- Marina A. GusevaMarina A. GusevaA.V. Topchiev Institute of Petrochemical Synthesis, RAS, 29 Leninskiy pr., Moscow 119991, RussiaMore by Marina A. Guseva
- ,
- Ivan V. NazarovIvan V. NazarovA.V. Topchiev Institute of Petrochemical Synthesis, RAS, 29 Leninskiy pr., Moscow 119991, RussiaMore by Ivan V. Nazarov
- ,
- Alexander A. MorontsevAlexander A. MorontsevA.V. Topchiev Institute of Petrochemical Synthesis, RAS, 29 Leninskiy pr., Moscow 119991, RussiaMore by Alexander A. Morontsev
- ,
- Gleb O. KarpovGleb O. KarpovA.V. Topchiev Institute of Petrochemical Synthesis, RAS, 29 Leninskiy pr., Moscow 119991, RussiaMore by Gleb O. Karpov
- ,
- Maxim A. TopchiyMaxim A. TopchiyA.V. Topchiev Institute of Petrochemical Synthesis, RAS, 29 Leninskiy pr., Moscow 119991, RussiaMore by Maxim A. Topchiy
- ,
- Andrey F. AsachenkoAndrey F. AsachenkoA.V. Topchiev Institute of Petrochemical Synthesis, RAS, 29 Leninskiy pr., Moscow 119991, RussiaMore by Andrey F. Asachenko
- ,
- Anastasia A. DanshinaAnastasia A. DanshinaA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Street, Moscow 119991, RussiaMoscow Institute of Physics and Technology (National Research University), Institutskiy per., 9, Dolgoprudny, Moscow Region 141701, RussiaMore by Anastasia A. Danshina
- ,
- Yulia V. NelyubinaYulia V. NelyubinaA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Street, Moscow 119991, RussiaMore by Yulia V. Nelyubina
- , and
- Maxim V. Bermeshev*Maxim V. Bermeshev*Email: [email protected]A.V. Topchiev Institute of Petrochemical Synthesis, RAS, 29 Leninskiy pr., Moscow 119991, RussiaMore by Maxim V. Bermeshev
Abstract
Well-defined single-component and tolerant Ru-, Mo-, and W-catalysts have been earlier developed for ring-opening metathesis polymerization of norbornene and its derivatives. Another way of norbornene polymerization─vinyl-addition polymerization (VAP)─is a more thermodynamically favorable process and gives polymers with saturated and rigid main chains. Single-component catalysts for VAP are required, which combine good activity, tolerance to functional groups, resistance to oxygen, and air moisture and are capable of catalyzing living VAP of norbornenes. Herein, we have shown that cationic Pd-complexes with N-heterocyclic carbene ligands (NHC ligands) and weak coordinating anion ligands ([(NHC)Pd(allyl)L]+A–, where allyl is an allyl group, L = CO, CH3CN, CH2Cl2, and A– = SbF6– or BARF–) are highly efficient single-component catalysts for VAP of both norbornene and various substituted norbornenes. These complexes, being stable in the solid state and in solutions, have exhibited several important features as VAP catalysts. They are capable of catalyzing VAP of norbornenes in air and are tolerant to functional groups. The complexes have shown high catalytic activity and have allowed polymerizing monomers at very low catalyst loadings, as low as 2 ppm. The versatility of [(NHC)Pd(allyl)L]+A– complexes as catalysts of VAP has been demonstrated by successful polymerization of monomers with polar and bulky groups, containing alkyl, vinyl, alkylidene, ether, ester, imide, or organosilicon motifs, affording high-molecular-weight products in good and high yields. Tuning the nature of NHC and allyl ligands in [(NHC)Pd(allyl)L]+A– complexes let perform living VAP, yielding block copolymers.
Cited By
This article has not yet been cited by other publications.