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Reactions of (PCP)Ir complexes with small molecules
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Title
Reactions of (PCP)Ir complexes with small molecules
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ETD_2271
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http://hdl.rutgers.edu/1782.2/rucore10001600001.ETD.000052125
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eng
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theses
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Chemistry
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Ligands
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Iridium catalysts
Abstract
Iridium pincer complexes (R4PCP)IrHn (PCP=[k3-2,6-C6H3(CH2PR2)]) are effective catalysts for the dehydrogenation of alkanes. We wished to design pincer ligands in which the set of phosphinoalkyl groups would offer (a) maximal steric "protection" against cluster-formation (b) minimal hindrance to C-H addition, and (c) resistance to decomposition and self-dehydrogenation (unlike iPr groups). Thus, we have synthesized iridium complexes of ligands tBu3MePCP ([C6H3(CH2PtBuMe)(CH2PtBu2]). (tBu3MePCP)IrH4 (1) shows more efficiency in dehydrogenation of alkanes than either
(tBu4PCP)IrHn or (iPr4MePCP)IrHn. (tBu3MePCP)IrH4 was also found to be a very effective catalyst in alkane metathesis.
Although isocyanides are important building blocks in organic synthesis, their commercial availability is limited compared to other chemicals. (PCP)Ir complexes react with different secondary methyl amines and at ambient temperature to form
corresponding iridium isocyanide complexes (PCP)Ir(H)(H)(CNR), 3-1 (a-e) which react with CO forming (PCP)Ir(CO) to liberate the corresponding isocyanide.
The addition of PhCCH to highly stable complexes, (PCP)IrL (L = CO, CNR), is challenging. (PCP)IrL (L = CO, CNR) complexes react with PhCCH in presence of acid to form complex (PCP)Ir(CO)(H)(CCPh) (5-3) and (PCP)Ir(CNBz)(H)(CCPh) (5-1), respectively, in which hydride and acetylide group are trans to each other. The reaction proceeds via the cationic intermediate [(PCP)Ir(CO)(H)]+. Solid-supported catalysts have significant advantages over homogeneous systems, particularly with respect to product-catalyst separation. We have investigated several routes to the development of supported pincer-ligated iridium catalysts. The p-dimethylamino- substituted PCP complex is found to bind strongly to alumina while maintaining the same high activity (or even slightly greater) for alkane-dehydrogenation as found in the solution phase.
A broad range of (PCP)Ir complexes with widely varying steric and electronic effects have been synthesized and studied including (PCP)IrL, (PCP)Ir(H)(H)L and PCP)Ir(H)(Cl)L, (L = various P- and N-donors, N2, various olefins). The relative thermodynamics of these adducts have been detected by equilibrium measurements and calculated using DFT. Precursors of "(PCP)Ir" cleaves sp3 C--O bonds of various esters (RCO2R1, R1= alkyl) to give (PCP)Ir(R1)(O2CR) or, in cases where R1 has a b-hydrogen, (PCP)Ir(H)(O2CR) plus the corresponding alkene derived from R1.
(tBu4PCP)IrHn or (iPr4MePCP)IrHn. (tBu3MePCP)IrH4 was also found to be a very effective catalyst in alkane metathesis.
Although isocyanides are important building blocks in organic synthesis, their commercial availability is limited compared to other chemicals. (PCP)Ir complexes react with different secondary methyl amines and at ambient temperature to form
corresponding iridium isocyanide complexes (PCP)Ir(H)(H)(CNR), 3-1 (a-e) which react with CO forming (PCP)Ir(CO) to liberate the corresponding isocyanide.
The addition of PhCCH to highly stable complexes, (PCP)IrL (L = CO, CNR), is challenging. (PCP)IrL (L = CO, CNR) complexes react with PhCCH in presence of acid to form complex (PCP)Ir(CO)(H)(CCPh) (5-3) and (PCP)Ir(CNBz)(H)(CCPh) (5-1), respectively, in which hydride and acetylide group are trans to each other. The reaction proceeds via the cationic intermediate [(PCP)Ir(CO)(H)]+. Solid-supported catalysts have significant advantages over homogeneous systems, particularly with respect to product-catalyst separation. We have investigated several routes to the development of supported pincer-ligated iridium catalysts. The p-dimethylamino- substituted PCP complex is found to bind strongly to alumina while maintaining the same high activity (or even slightly greater) for alkane-dehydrogenation as found in the solution phase.
A broad range of (PCP)Ir complexes with widely varying steric and electronic effects have been synthesized and studied including (PCP)IrL, (PCP)Ir(H)(H)L and PCP)Ir(H)(Cl)L, (L = various P- and N-donors, N2, various olefins). The relative thermodynamics of these adducts have been detected by equilibrium measurements and calculated using DFT. Precursors of "(PCP)Ir" cleaves sp3 C--O bonds of various esters (RCO2R1, R1= alkyl) to give (PCP)Ir(R1)(O2CR) or, in cases where R1 has a b-hydrogen, (PCP)Ir(H)(O2CR) plus the corresponding alkene derived from R1.
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xxvi, 288 p. : ill.
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Ph.D.
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by Sabuj Kumar Kundu
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Sabuj Kumar
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1981-
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Sabuj Kumar Kundu
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Goldman
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Alan
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Alan S Goldman
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Krogh- Jespersen
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Karsten
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Karsten Krogh- Jespersen
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Warmuth
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Ralf
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Ralf Warmuth
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Glasser
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Benjamin J Glasser
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Rutgers University
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Graduate School - New Brunswick
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2010
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2010-01
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xx
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Rutgers University Electronic Theses and Dissertations
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Graduate School - New Brunswick Electronic Theses and Dissertations
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doi:10.7282/T3ZS2WNR
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ETD doctoral
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The author owns the copyright to this work.
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Open
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Kundu
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Sabuj
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2009-12-03 10:14:35
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Sabuj Kundu
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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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