Probing the Characteristics of Mono- or Bimetallic (Iron or Cobalt) Complexes Bearing 2,4-Bis(6-iminopyridin-2-yl)-3H-benzazepines: Synthesis, Characterization, and Ethylene Reactivity

Abstract

A series of 2,4-bis(6-iminopyridin-2-yl)-3H-benzazepines and the mono-or bimetallic (Fe 2+ or Co 2+ ) complexes thereof were synthesized and characterized. All title complexes, when activated by MAO or MMAO, exhibited high activities of up to 4.0 × 10 7 g (mol of Fe) −1 h −1 for ethylene oligomerization and polymerization. The iron(II) precatalysts generally showed higher activities and produced a wider distribution of products (including oligomers and polyethylene) than did their corresponding cobalt(II) analogues. The bimetallic precatalysts exhibited higher (almost twice) activities in comparison to their monometallic analogues. The distribution of the resulting oligomers closely resembled the Schultz−Flory rule.

Pyridine–oxazoline and quinoline–oxazoline ligated cobalt complexes: Synthesis, characterization, and 1,3-butadiene polymerization behaviors

“…In recent years, research interest has been focused on the design and synthesis of well-defined single-site catalysts in order to gain precise control of the catalysis behavior and polymer composition [12][13][14][15]. Since the discovery of bis(arylimino)pyridine ligated Co(II) and iron(II) complexes as effective catalysts for ethylene polymerization/oligomerization [16,17], a variety of transition metal complexes bearing α-diimine, pyridinediimine, and their derivatives have been synthesized and exploited as catalyst precursors for olefin polymerization [18][19][20][21][22][23][24].…”

Developments in compartmentalized bimetallic transition metal ethylene polymerization catalysts

“…As with the linked diimine-nickel precatalysts discussed in the previous section, there have been a number of investigations concerned with developing bimetallic iron or cobalt catalysts that incorporate two bis(imino)pyridine binding pockets within the same compartmental ligand [83][84][85][86][87][88]. Indeed, a wide variety of synthetic strategies have been employed including the use of di-aniline units as building blocks in the condensation protocol [89][90][91][92][93].…”

Modelling chemical kinetics of a complex reaction network of active pharmaceutical ingredient (API) synthesis with process optimization for benzazepine heterocyclic compound

“…The literature on the kinetics of the reactions to-and of benzazepine heterocyclic compounds [25][26][27] does not provide a suitable background to compare reaction rate constants, let alone preexponential factors or activation energies. Nonetheless, when comparing the determined partial AA order (and thus also the mechanism of pathways, illustrated in Fig.…”

“…Due to the absence of any relevant literature data on lorcaserin-, or even more generally, benzazepine-related reaction kinetics, not to mention the vastly different conditions or even its further transformations [25][26][27], the main aim of the current work was to perform a kinetic study, so that it would in turn support an improved scale-up prediction, process optimization and understanding. The latter was done by developing the mechanism-based kinetic models of synthesis reaction steps and utilizing them to optimize process yields.…”