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Lynda K. Johnson

Other affiliations: DuPont Central Research
Bio: Lynda K. Johnson is an academic researcher from University of North Carolina at Chapel Hill. The author has contributed to research in topics: Diimine & Migratory insertion. The author has an hindex of 9, co-authored 12 publications receiving 6634 citations. Previous affiliations of Lynda K. Johnson include DuPont Central Research.

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TL;DR: In this article, the effects of reaction conditions and catalyst structure on the copolymerization reaction were rationalized, and the effect of the acrylate comonomer at the ends of branches as −CH2CH2C(O)OMe groups was analyzed.
Abstract: Mechanistic aspects of palladium-catalyzed insertion copolymerizations of ethylene and α-olefins with methyl acrylate to give high molar mass polymers are described. Complexes [(N∧N)Pd(CH2)3C(O)OMe]BAr‘4 (2) or [(N∧N)Pd(CH3)(L)]BAr‘4 (1: L = OEt2; 3: L ⋮ NCMe; 4: L ⋮ NCAr‘) (N∧N ≡ ArNC(R)−C(R)NAr, e.g., Ar ⋮ 2,6-C6H3(i-Pr)2, R ⋮ H (a), Me (b); Ar‘ ⋮ 3,5-C6H3(CF3)2) with bulky substituted α-diimine ligands were used as catalyst precursors. The copolymers are highly branched, the acrylate comonomer being incorporated predominantly at the ends of branches as −CH2CH2C(O)OMe groups. The effects of reaction conditions and catalyst structure on the copolymerization reaction are rationalized. Low-temperature NMR studies show that migratory insertion in the η2-methyl acrylate (MA) complex [(N∧N)PdMe{H2CCHC(O)OMe}]+ (5) occurs to give initially the 2,1-insertion product [(N∧N)PdCH(CH2CH3)C(O)OMe]+ (6), which rearranges stepwise to yield 2 as the final product upon warming to −20 °C. Activation parameters (ΔH⧧ = ...

857 citations

Journal ArticleDOI
TL;DR: In this article, mechanistic studies of olefin polymerizations catalyzed by aryl-substituted α-diimine−Pd(II) complexes are presented.
Abstract: Mechanistic studies of olefin polymerizations catalyzed by aryl-substituted α-diimine−Pd(II) complexes are presented. Syntheses of several cationic catalyst precursors, [(N∧N)Pd(CH3)(OEt2)]BAr‘4 (N∧N = aryl-substituted α-diimine, Ar‘ = 3,5-(CF3)2C6H3), are described. X-ray structural analyses of [ArNC(H)C(H)NAr]Pd(CH3)(Cl) and [ArNC(Me)C(Me)NAr]Pd(CH3)2 (Ar = 2,6-(iPr)2C6H3) illustrate that o-aryl substituents crowd axial sites in these square planar complexes. Low-temperature NMR studies show that the alkyl olefin complexes, (N∧N)Pd(R)(olefin)+, are the catalyst resting states and that the barriers to migratory insertions lie in the range 17−19 kcal/mol. Following migratory insertion, the cationic palladium alkyl complexes (N∧N)Pd(alkyl)+ formed are β-agostic species which exhibit facile metal migration along the chain (“chain walking”) via β-hydride elimination/readdition reactions. Model studies using palladium−n-propyl and −isopropyl systems provide mechanistic details of this process, which is respon...

509 citations


Cited by
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TL;DR: The graph below shows the progression of monoanionic and non-monoanionic ligands through the history of synthesis, as well as some of the properties that have been identified since the discovery of R-Diimine.
Abstract: B. Anionic Ligands 302 IX. Group 9 Catalysts 302 X. Group 10 Catalysts 303 A. Neutral Ligands 303 1. R-Diimine and Related Ligands 303 2. Other Neutral Nitrogen-Based Ligands 304 3. Chelating Phosphorus-Based Ligands 304 B. Monoanionic Ligands 305 1. [PO] Chelates 305 2. [NO] Chelates 306 3. Other Monoanionic Ligands 306 4. Carbon-Based Ligands 306 XI. Group 11 Catalysts 307 XII. Group 12 Catalysts 307 XIII. Group 13 Catalysts 307 XIV. Summary and Outlook 308 XV. Glossary 308 XVI. References 308

2,369 citations

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TL;DR: Commercialization of new generations of single-site and metallocene catalyst-based technologies has provided the multibillion pound per year polyolefins industry with the ability to deliver a wide range of new and innovative olefin-based polymers having improved properties.
Abstract: One of the most exciting developments in the areas of catalysis, organometallic chemistry, and polymer science in recent years has been the intense exploration and commercialization of new polymerization technologies based on single-site and metallocene coordination olefin polymerization catalysts.1 The vast number of specifically designed/synthesized transition metal complexes (catalyst precursors) and main-group organometallic compounds (cocatalysts) allows unprecedented control over polymer microstructure, the generation of new polymer architectures, and the development of new polymerization reactions. Commercialization of new generations of single-site and metallocene catalyst-based technologies has provided the multibillion pound per year polyolefins industry with the ability to deliver a wide range of new and innovative olefin-based polymers having improved properties.2-4 The intense industrial activity in the field and the challenges to our basic understanding that have come to light have in turn 1391 Chem. Rev. 2000, 100, 1391−1434

1,719 citations