α‐Diimine–Palladium Complexes Incorporated in Vinylic‐Addition Polynorbornenes: Synthesis and Catalytic Activity

Abstract

α-Diimine polymeric ligands have been synthesized using the bicyclic norbornane structure, present in vinylic addition polynorbornene (VA-PNB). The VA-PNB-diimine ligands have been prepared by functionalization of the copolymer obtained by the Nicatalyzed polymerization of norbornene and norbornenylcarbonate. Immobilized palladium complexes of the type VA-PNB-diimine-PdX2 have been prepared and their catalytic activity tested. The trifluoroacetato complex (X = CF3COO) can be used as a recyclable precatalyst in the Suzuki reaction. It is the source of minute amounts of homogeneous palladium active species that carry out the catalysis with high turnover numbers. The recovered polymeric complex can be reused several times with no significant loss of activity. The polymeric analogue to Brookhart´s catalyst, VA-PNB-diiminePdMeCl, can also polymerize ethylene, although it is less active than their monomeric counterparts.

Polymerization of 5-Alkylidene-2-norbornenes with Highly Active Pd–N-Heterocyclic Carbene Complex Catalysts: Catalyst Structure–Activity Relationships

“…The addition polynorbornenes with different side groups are of interest as photoresists, , membrane materials, − dielectrics, , nonlinear optical materials, adhesives, organic light emitting diodes, , porous organic polymers, , and so forth. The synthesis of addition polynorbornenes with reactive side groups opens new possibilities for the macromolecular design of polymeric materials possessing desired properties by the targeted modifications of side-substituents in addition polymers. , In some cases, it is difficult to perform the selective polymerization of norbornenes containing reactive groups, which can inhibit the catalyst activity or take part in the polymerization leading to crosslinked polymeric products. Thus, a search for selective and tolerant catalytic systems for the addition polymerization of norbornenes bearing reactive groups is a problem of considerable current interest.…”

Trispyrazolylborate Ligands Supported on Vinyl Addition Polynorbornenes and Their Copper Derivatives as Recyclable Catalysts

“…We have previously used VA‐PNB‐based polymers as supports for catalysts bearing other donor ligands such as N‐heterocyclic carbenes . We also have supported organotin reagents and used them in palladium‐catalyzed Stille couplings, and radical reactions, with good recyclability and the additional advantage of leaving a very low tin contamination in the products.…”

Macromolecular Design and Synthesis of Polymers from Silicon- Containing Norbornenes for Membrane Gas Separation

“…Several transition metal complexes ((η 6toluene)Ni(C 6 F 5 ) 2 [94][95][96], Ni(SbPh 3 ) 2 (C 6 F 5 ) 2 [97][98], [Pd(MeCN) 4 ](BF 4 ) 2 [99][100]) were shown to catalyze the addition polymerization of norbornene derivatives without the application of cocatalysts (the so-called single-component catalysts). However, usually two-or three-component systems (based on the Pd or Ni compounds (precatalysts), B or/and Al organic derivatives (cocatalysts), and sometimes including a phosphine (like triphenylphosphine or tricyclohexylphosphine)) are used as the catalysts in addition polymerization of norbornenes [42][43][101][102][103].…”