Synthesis of Chromium, Iron, and Nickel Complexes Using Aryl-based Chelates as Ancillary Ligands and a Series of Bis([alpha]-iminopyridyl) Iron Compounds with Varying Donor Ligands PDF Download
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Author: Emily C. Volpe
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Languages : en
Pages : 0
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Several classes of aryl-based chelates containing pyridine, oxazoline, or imine donors and their reactivity with 1st-row transition metals were investigated in light of the potential of carbon-based ligands to impart strong ligand fields. Heterolytic C-H bond activation of 2-phenylpyridine was achieved with Ni(OTf)2. The cyclometalated product and its derivatives undergo substitution, insertion, and additional cyclometalation reactions. Aryl-oxazolines display a range of reactivity patterns which are dependent on the reaction conditions, the metal, and the particular ligand employed. Aryl-aryl coupling, oxazoline ring-opening, and methylene deprotonation were examined, but were tangential to the goal of making metal-aryl bonds. Successful arylation of nickel, iron and chromium was accomplished using a methylated benzyl-oxazoline aryl anion, and the spectroscopic, structural, and magnetic properties of these complexes are described. Tridentate arylpyridylimines or diarylimines undergo facile arylation with cis-(Me3P)4Fe(Me)2 to give low-spin, sixcoordinate iron compounds. Their thermal and oxidation behavior are studied, and the spectroscopic properties of their azaallyl derivatives are compared to previouslyreported, related species. A highly-fluorinated congener of the diarylimine iron complexes was sought, and preliminary evidence of its divergent reactivity is noted. Finally, a series of iminopyridine complexes of the formula (N,N'-[alpha]- iminopyridyl)2Fe(L/X)n have been examined by X-ray and Mossbauer spectroscopy. The redox-active nature of the iminopyridine ligands and the donating ability of the additional L/X ligands have been assessed.
![Synthesis of Chromium, Iron, and Nickel Complexes Using Aryl-based Chelates as Ancillary Ligands and a Series of Bis([alpha]-iminopyridyl) Iron Compounds with Varying Donor Ligands PDF](https://books.google.com/books/content/images/frontcover/i9arzwEACAAJ?fife=w80-h100)
Author: Emily C. Volpe
Publisher:
ISBN:
Category :
Languages : en
Pages : 0
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Book Description
Several classes of aryl-based chelates containing pyridine, oxazoline, or imine donors and their reactivity with 1st-row transition metals were investigated in light of the potential of carbon-based ligands to impart strong ligand fields. Heterolytic C-H bond activation of 2-phenylpyridine was achieved with Ni(OTf)2. The cyclometalated product and its derivatives undergo substitution, insertion, and additional cyclometalation reactions. Aryl-oxazolines display a range of reactivity patterns which are dependent on the reaction conditions, the metal, and the particular ligand employed. Aryl-aryl coupling, oxazoline ring-opening, and methylene deprotonation were examined, but were tangential to the goal of making metal-aryl bonds. Successful arylation of nickel, iron and chromium was accomplished using a methylated benzyl-oxazoline aryl anion, and the spectroscopic, structural, and magnetic properties of these complexes are described. Tridentate arylpyridylimines or diarylimines undergo facile arylation with cis-(Me3P)4Fe(Me)2 to give low-spin, sixcoordinate iron compounds. Their thermal and oxidation behavior are studied, and the spectroscopic properties of their azaallyl derivatives are compared to previouslyreported, related species. A highly-fluorinated congener of the diarylimine iron complexes was sought, and preliminary evidence of its divergent reactivity is noted. Finally, a series of iminopyridine complexes of the formula (N,N'-[alpha]- iminopyridyl)2Fe(L/X)n have been examined by X-ray and Mossbauer spectroscopy. The redox-active nature of the iminopyridine ligands and the donating ability of the additional L/X ligands have been assessed.
Author: Anthony Kermagoret
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Languages : en
Pages :
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Book Description
My Ph-D thesis concerns the study of the catalytic oligomerization reaction with nickel, iron and cobalt complexes coordinated by N-O, P-N, N-P-N, P-O and P-N-P type ligands with a N donor atom represented by an oxazoline or a pyridine heterocycle. These complexes activated by a cocatalyst such as MAO or AlEtCl2 showed high activities and a high selectivity of C4 olefins in ethylene oligomerization. The nickel complexes with P-N chelates showed a high impact of the P substituents on the oligomerization selectivities. Moreover, the crystallographic studies on nickel complexes coordinated by N-O and P-N type ligands showed the formation of mono-, di- and tetranuclear complexes. The cobalt, iron and palladium complexes with N-P-N ligands highlighted original N-N, P-N or N-P-N coordination modes of the ligands influenced by the ligand substituents and the metal center.
