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Studies of PNP and PCP pincer complexes: synthesis and C-H activation potential of PNP pincer complexes and a PCP pincer complex applied to alkene hydrogenation
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Title
Studies of PNP and PCP pincer complexes: synthesis and C-H activation potential of PNP pincer complexes and a PCP pincer complex applied to alkene hydrogenation
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Title
Synthesis and C-H activation potential of PNP pincer complexes and a PCP pincer complex applied to alkene hydrogenation
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Pelczar
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Elizabeth M.
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Elizabeth M. Pelczar
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Goldman
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Alan
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Advisory Committee
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Alan S Goldman
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Krogh-Jespersen
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Karsten
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Advisory Committee
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Karsten Krogh-Jespersen
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internal member
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Brennan
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John
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Advisory Committee
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John Brennan
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Sheridan
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John
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Advisory Committee
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John Sheridan
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Rutgers University
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Graduate School - New Brunswick
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theses
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2008
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2008-01
Language
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English
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electronic
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text/xml
Extent
xiii, 188 pages
Abstract
The ability to break the C-H bond, which is considered one of the most inert bonds in chemistry, has vast applications in a wide variety of chemical processes. (RPCP)Ir pincer complexes have been shown to be highly effective catalysts for C-H activation, in particular in the context of dehydrogenation reactions. Related to the (RPCP)Ir complexes are (RPNP)M complexes which have not been examined in terms of C-H activation potential.
Chapter 2 presents the synthesis and full characterization of two new iron PNP pincer complexes, (tBuPNP)FeCl2 and (tBuPNP)Fe(CO)2. The dichloride complex is paramagnetic with an unusually long Fe-N bond. The blue dicarbonyl complex has significantly bent Fe-C-O angles in the solid state and in solution, and appears to be an equilibrium mixture between square pyramidal and trigonal bipyramidal structures.
Chapter 3 presents the synthesis and full characterization of two new osmium tBuPNP pincer complexes, (tBuPNP)OsCl3 and (tBuPNP)OsH4. The crystal structure of the hydride complex shows that the complex is a purely classical hydride in the solid state.
Chapter 4 follows up on (tBuPNP)OsH4 by discussing the reactivity of this complex. Unlike the (RPCP)Ir complexes, (tBuPNP)OsH4 was not found to be an active catalyst for C-H activation, dehydrogenation, or phenylacetylene dimerization. The difference in reactivity most likely comes from the difference in metal-hydride bond strength.
Chapter 5 discusses the hydrogenation kinetics of trans-5-decene by (tBuPCP)IrH2. The reaction follows second order kinetics and appears to be largely temperature independent. The room temperature activation energy, activation enthalpy, and activation entropy were calculated and show that the main barrier comes from entropic factors.
Chapter 6 presents the synthesis and characterization of a new (tBuPCP)IrH-ยต2-Cl2-Ir(COD) dimer. This complex can be thought of as the oxidative addition product of (tBuPCP) with 1/2 [Ir(COD)Cl]2. The complex was found to be an Ir(I) / Ir(III) dimer with the hydride atom coordinated to the Ir(III) atom that was coordinated to the PCP ligand.
Chapter 2 presents the synthesis and full characterization of two new iron PNP pincer complexes, (tBuPNP)FeCl2 and (tBuPNP)Fe(CO)2. The dichloride complex is paramagnetic with an unusually long Fe-N bond. The blue dicarbonyl complex has significantly bent Fe-C-O angles in the solid state and in solution, and appears to be an equilibrium mixture between square pyramidal and trigonal bipyramidal structures.
Chapter 3 presents the synthesis and full characterization of two new osmium tBuPNP pincer complexes, (tBuPNP)OsCl3 and (tBuPNP)OsH4. The crystal structure of the hydride complex shows that the complex is a purely classical hydride in the solid state.
Chapter 4 follows up on (tBuPNP)OsH4 by discussing the reactivity of this complex. Unlike the (RPCP)Ir complexes, (tBuPNP)OsH4 was not found to be an active catalyst for C-H activation, dehydrogenation, or phenylacetylene dimerization. The difference in reactivity most likely comes from the difference in metal-hydride bond strength.
Chapter 5 discusses the hydrogenation kinetics of trans-5-decene by (tBuPCP)IrH2. The reaction follows second order kinetics and appears to be largely temperature independent. The room temperature activation energy, activation enthalpy, and activation entropy were calculated and show that the main barrier comes from entropic factors.
Chapter 6 presents the synthesis and characterization of a new (tBuPCP)IrH-ยต2-Cl2-Ir(COD) dimer. This complex can be thought of as the oxidative addition product of (tBuPCP) with 1/2 [Ir(COD)Cl]2. The complex was found to be an Ir(I) / Ir(III) dimer with the hydride atom coordinated to the Ir(III) atom that was coordinated to the PCP ligand.
Note
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Ph.D.
Note
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Includes bibliographical references.
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Chemistry and Chemical Biology
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Ligands
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Topic
Ligand binding (Biochemistry)
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Topic
Metal complexes
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(ID = SUBJ5);
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Organometallic compounds
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Graduate School - New Brunswick Electronic Theses and Dissertations
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doi:10.7282/T32807ZX
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ETD doctoral
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Elizabeth Pelczar
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Rutgers University. Graduate School - New Brunswick
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I hereby grant to the Rutgers University Libraries and to my school the non-exclusive right to archive, reproduce and distribute my thesis or dissertation, in whole or in part, and/or my abstract, in whole or in part, in and from an electronic format, subject to the release date subsequently stipulated in this submittal form and approved by my school. I represent and stipulate that the thesis or dissertation and its abstract are my original work, that they do not infringe or violate any rights of others, and that I make these grants as the sole owner of the rights to my thesis or dissertation and its abstract. I represent that I have obtained written permissions, when necessary, from the owner(s) of each third party copyrighted matter to be included in my thesis or dissertation and will supply copies of such upon request by my school. I acknowledge that RU ETD and my school will not distribute my thesis or dissertation or its abstract if, in their reasonable judgment, they believe all such rights have not been secured. I acknowledge that I retain ownership rights to the copyright of my work. I also retain the right to use all or part of this thesis or dissertation in future works, such as articles or books.
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