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ucin1085526904.pdf (7.46 MB)
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INVESTIGATION OF NICKEL (II)-OXIMATE COMPLEXES THAT REACT WITH MOLECULAR OXYGEN
Author Info
EDISON, SARA ELIZABETH
Permalink:
http://rave.ohiolink.edu/etdc/view?acc_num=ucin1085526904
Abstract Details
Year and Degree
2004, PhD, University of Cincinnati, Arts and Sciences : Chemistry.
Abstract
Ni(II) complexes containing amidates and thiolates have been shown to react with O2 via irreversible ligand oxidation. We have constructed a series of Ni(II) complexes based on a tripodal amine bis(oxime) ligand framework. These complexes display oxygen reactivity upon deprotonation of the oximes without requiring irreversible ligand oxidation. This project investigated the reaction involving one of the complexes in the library, [Ni(TRISOXH
3
)(NO
3
)(H
2
O)](NO
3
)· (H
2
O), where TRISOXH
3
= (tris(1-propan-2-onyl oxime)amine). It was discovered that the reaction of this complex with molecular oxygen is contingent upon the presence of a source of hydrogen atoms. This two-hydrogen atom donor acts as a substrate. Several primary alcohols, including the relatively inert methanol, and amines were catalytically oxidized by this reaction. Spectroscopic analysis using a variety of techniques has demonstrated that reversible oxidation occurs on the oximate nitrogen to form an iminoxyl radical. Many of the other complexes in the series were also investigated to examine their electronic structure, their electrochemical properties, and their ability to oxidize methanol.
Committee
Dr. Michael Baldwin (Advisor)
Pages
197 p.
Subject Headings
Chemistry, Inorganic
Keywords
Nickel(II)
;
oximes
;
oxygen activation
;
substrate oxidation
;
catalysis
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Citations
EDISON, S. E. (2004).
INVESTIGATION OF NICKEL (II)-OXIMATE COMPLEXES THAT REACT WITH MOLECULAR OXYGEN
[Doctoral dissertation, University of Cincinnati]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1085526904
APA Style (7th edition)
EDISON, SARA.
INVESTIGATION OF NICKEL (II)-OXIMATE COMPLEXES THAT REACT WITH MOLECULAR OXYGEN.
2004. University of Cincinnati, Doctoral dissertation.
OhioLINK Electronic Theses and Dissertations Center
, http://rave.ohiolink.edu/etdc/view?acc_num=ucin1085526904.
MLA Style (8th edition)
EDISON, SARA. "INVESTIGATION OF NICKEL (II)-OXIMATE COMPLEXES THAT REACT WITH MOLECULAR OXYGEN." Doctoral dissertation, University of Cincinnati, 2004. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1085526904
Chicago Manual of Style (17th edition)
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Document number:
ucin1085526904
Download Count:
1,056
Copyright Info
© 2004, all rights reserved.
This open access ETD is published by University of Cincinnati and OhioLINK.