Nitric oxide reactivity of manganese, iron and cobalt tropocoronands and development of fluorescent aminotroponiminates for nitric oxide sensing

Chapter 1. Environmental and Biological Implications of Transition Metal-Nitric Oxide Interactions. This introductory chapter reviews various aspects of NO reactivity by transition metals and in biological systems. Chapter 2. Disproportionation of Nitric Oxide Promoted by a Mn Tropocoronand The first example of a manganese-induced nitric oxide (NO) disproportionation reaction is reported. The synthesis and characterization of divalent [Mn(THF)(TC-5,5)] (1) is presented, along with its reactivity with excess NO to yield N20 and [Mn(NO2)(TC-5,5)] (2). The NO disproportionation involves the formation of a discrete mononitrosyl [Mn(NO)(TC-5,5)j (3), which has been isolated and characterized formally as (MnmNO-) by infrered spectroscopy, normal coordinate analysis, X-ray crystallography and SQUID susceptometry. Chapter 3. NO Disproportionation Reactivity of Fe Tropocoronand Complexes The synthesis and characterization of divalent [Fe(TC-5,5)] (1) and trivalent [Fe(OTf)(TC-5,5)] (2) tropocoronand complexes are described. Compound 1 reacts with one equivalent of NO to form the trigonal bipyramidal (FeNO)7 complex 3, which contains a linearly coordinated nitrosyl (Fe-N-O = 174.3(4)). EPR and M6ssbauer spectroscopy, SQUID susceptometry and normal coordinate analysis indicate 3 to be a low spin (Fem(NO-))2 species. In the presence of excess NO, 3 converts to a metastable nitrosyl-nitrito complex that decomposes by losing NO2. The final products of the NO disproportionation reaction are N2O and [Fe(NO)(TC-5,5-NO2)] (4), a compound that no longer promotes the disproportionation of NO. Mechanistic aspects of the reaction are discussed. Chapter 4. Aminotroponiminates as Ligands for Potential Metal-Based NO Sensors. Part I. Synthesis and Characterization Fluorescently labeled ligands, HRDATI, are described that are composed of aminotroponiminates (ATI) with a dansyl fluorophore on one of the imine nitrogen atoms and an alkyl substituent on the other.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2000

Author dc:creator

• Franz, Katherine J. (Katherine Jennings), 1972-

Advisor dc:contributor.advisor

• Stephen J. Lippard.

• Chemistry.

Statement dc:rights

• M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/29590

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/29590