ingest cdrApp 2018-06-13T16:31:34.479Z 51cd2fe2-3fd7-401f-a923-a97bc3db68a2 modifyDatastreamByValue RELS-EXT fedoraAdmin 2018-06-13T16:58:49.746Z Setting exclusive relation addDatastream MD_TECHNICAL fedoraAdmin 2018-06-13T16:59:00.958Z Adding technical metadata derived by FITS addDatastream MD_FULL_TEXT fedoraAdmin 2018-06-13T16:59:24.665Z Adding full text metadata extracted by Apache Tika modifyDatastreamByValue RELS-EXT fedoraAdmin 2018-06-13T16:59:46.936Z Setting exclusive relation modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-07-11T20:43:42.190Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-07-18T15:44:42.571Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-08-22T14:19:04.204Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-09-28T16:56:47.702Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-10-12T16:02:18.153Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2019-03-22T19:18:49.486Z Javier Grajeda Author Department of Chemistry College of Arts and Sciences PINCER COMPLEXES OF PRECIOUS METALS The synthesis and characterization of several new iridium(I) and iridium(III) carbonyl complexes supported by aminophosphinite pincer ligands is reported. A surprising diversity of reaction pathways were accessible upon treatment of Ir carbonyl complexes with salts of redox-inactive alkali, alkaline earth, and lanthanide metal cations. Iridium(III) hydridocarbonyl chloride complexes underwent either halide abstraction or halide substitution reactions, whereas iridium(I) carbonyl complexes underwent protonative oxidative addition reactions. When the nitrogen donor of the pincer ligand is an aza-crown ether macrocycle, cation–macrocycle interactions can be supported, leading to divergent reactivity in some cases. New iridium and rhodium complexes supported by aminophosphinite pincer-crown ether ligands were synthesized. Iridium-catalyzed hydroformylation of allylbenzene was explored. Catalytic amounts of LiOTf (OTf = trifluoromethanesulfonate) doubled the rate of hydrofunctionalization. The iridium pincer complexes were found to undergo remetallation pathways under the conditions of catalysis. This guided the design of a new, more active iridium catalyst supported by a pincer ligand with a methoxy substituent incorporated to prevent remetallation. Rhodium-catalyzed hydroformylation of 1-octene was explored as well. A systematic decrease in the n (linear) to iso (branched) aldehyde ratio was observed in the presence of increasingly bulky ammonium additives. However, catalyst stability studies showed that rhodium pincer complexes undergo decomposition under hydroformylation conditions and presumably simply act as pre-catalysts. The first mononuclear gold(III) PNP pincer complexes (PNP = bis(2- diisopropylphosphinophenyl)amide) are reported. The chloro complex [(PNP)Au(Cl)][OAcF] (OAcF = OCOCF3) was synthesized by microwave irradiation of a tetrachloroaurate salt and the neutral PNHP ligand. Dehalogenation with AgOAcF afforded the trifluoroacetate-bound complex [(PNP)Au(OAcF)][OAcF]. Electronic absorption spectroscopy and time-dependent density functional theory studies assigned the electronic transition that imbues the complexes with a deep royal blue color. The Au(III) trifluoroacetate complex is surprisingly stable, and no reactivity towards ethylene was observed, even under high pressures and at high temperatures. Density functional theory calculations suggest that the lack of reactivity is due to the high energy of the putative dicationic ethylene-bound intermediate invoked in a formal insertion reaction. Spring 2018 2018 Chemistry eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry Alexander Miller Thesis advisor Thomas Meyer Thesis advisor Gerald Meyer Thesis advisor Frank Leibfarth Thesis advisor Jeffrey Johnson Thesis advisor text Javier Grajeda Author Department of Chemistry College of Arts and Sciences PINCER COMPLEXES OF PRECIOUS METALS The synthesis and characterization of several new iridium(I) and iridium(III) carbonyl complexes supported by aminophosphinite pincer ligands is reported. A surprising diversity of reaction pathways were accessible upon treatment of Ir carbonyl complexes with salts of redox-inactive alkali, alkaline earth, and lanthanide metal cations. Iridium(III) hydridocarbonyl chloride complexes underwent either halide abstraction or halide substitution reactions, whereas iridium(I) carbonyl complexes underwent protonative oxidative addition reactions. When the nitrogen donor of the pincer ligand is an aza-crown ether macrocycle, cation–macrocycle interactions can be supported, leading to divergent reactivity in some cases. New iridium and rhodium complexes supported by aminophosphinite pincer-crown ether ligands were synthesized. Iridium-catalyzed hydroformylation of allylbenzene was explored. Catalytic amounts of LiOTf (OTf = trifluoromethanesulfonate) doubled the rate of hydrofunctionalization. The iridium pincer complexes were found to undergo remetallation pathways under the conditions of catalysis. This guided the design of a new, more active iridium catalyst supported by a pincer ligand with a methoxy substituent incorporated to prevent remetallation. Rhodium-catalyzed hydroformylation of 1-octene was explored as well. A systematic decrease in the n (linear) to iso (branched) aldehyde ratio was observed in the presence of increasingly bulky ammonium additives. However, catalyst stability studies showed that rhodium pincer complexes undergo decomposition under hydroformylation conditions and presumably simply act as pre-catalysts. The first mononuclear gold(III) PNP pincer complexes (PNP = bis(2- diisopropylphosphinophenyl)amide) are reported. The chloro complex [(PNP)Au(Cl)][OAcF] (OAcF = OCOCF3) was synthesized by microwave irradiation of a tetrachloroaurate salt and the neutral PNHP ligand. Dehalogenation with AgOAcF afforded the trifluoroacetate-bound complex [(PNP)Au(OAcF)][OAcF]. Electronic absorption spectroscopy and time-dependent density functional theory studies assigned the electronic transition that imbues the complexes with a deep royal blue color. The Au(III) trifluoroacetate complex is surprisingly stable, and no reactivity towards ethylene was observed, even under high pressures and at high temperatures. Density functional theory calculations suggest that the lack of reactivity is due to the high energy of the putative dicationic ethylene-bound intermediate invoked in a formal insertion reaction. Spring 2018 2018 Chemistry eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry Alexander Miller Thesis advisor Thomas Meyer Thesis advisor Gerald Meyer Thesis advisor Frank Leibfarth Thesis advisor Jeffrey Johnson Thesis advisor text Javier Grajeda Author Department of Chemistry College of Arts and Sciences PINCER COMPLEXES OF PRECIOUS METALS The synthesis and characterization of several new iridium(I) and iridium(III) carbonyl complexes supported by aminophosphinite pincer ligands is reported. A surprising diversity of reaction pathways were accessible upon treatment of Ir carbonyl complexes with salts of redox-inactive alkali, alkaline earth, and lanthanide metal cations. Iridium(III) hydridocarbonyl chloride complexes underwent either halide abstraction or halide substitution reactions, whereas iridium(I) carbonyl complexes underwent protonative oxidative addition reactions. When the nitrogen donor of the pincer ligand is an aza-crown ether macrocycle, cation–macrocycle interactions can be supported, leading to divergent reactivity in some cases. New iridium and rhodium complexes supported by aminophosphinite pincer-crown ether ligands were synthesized. Iridium-catalyzed hydroformylation of allylbenzene was explored. Catalytic amounts of LiOTf (OTf = trifluoromethanesulfonate) doubled the rate of hydrofunctionalization. The iridium pincer complexes were found to undergo remetallation pathways under the conditions of catalysis. This guided the design of a new, more active iridium catalyst supported by a pincer ligand with a methoxy substituent incorporated to prevent remetallation. Rhodium-catalyzed hydroformylation of 1-octene was explored as well. A systematic decrease in the n (linear) to iso (branched) aldehyde ratio was observed in the presence of increasingly bulky ammonium additives. However, catalyst stability studies showed that rhodium pincer complexes undergo decomposition under hydroformylation conditions and presumably simply act as pre-catalysts. The first mononuclear gold(III) PNP pincer complexes (PNP = bis(2- diisopropylphosphinophenyl)amide) are reported. The chloro complex [(PNP)Au(Cl)][OAcF] (OAcF = OCOCF3) was synthesized by microwave irradiation of a tetrachloroaurate salt and the neutral PNHP ligand. Dehalogenation with AgOAcF afforded the trifluoroacetate-bound complex [(PNP)Au(OAcF)][OAcF]. Electronic absorption spectroscopy and time-dependent density functional theory studies assigned the electronic transition that imbues the complexes with a deep royal blue color. The Au(III) trifluoroacetate complex is surprisingly stable, and no reactivity towards ethylene was observed, even under high pressures and at high temperatures. Density functional theory calculations suggest that the lack of reactivity is due to the high energy of the putative dicationic ethylene-bound intermediate invoked in a formal insertion reaction. Spring 2018 2018 Chemistry eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry Alexander Miller Thesis advisor Thomas Meyer Thesis advisor Gerald Meyer Thesis advisor Frank Leibfarth Thesis advisor Jeffrey Johnson Thesis advisor text Javier Grajeda Author Department of Chemistry College of Arts and Sciences PINCER COMPLEXES OF PRECIOUS METALS The synthesis and characterization of several new iridium(I) and iridium(III) carbonyl complexes supported by aminophosphinite pincer ligands is reported. A surprising diversity of reaction pathways were accessible upon treatment of Ir carbonyl complexes with salts of redox-inactive alkali, alkaline earth, and lanthanide metal cations. Iridium(III) hydridocarbonyl chloride complexes underwent either halide abstraction or halide substitution reactions, whereas iridium(I) carbonyl complexes underwent protonative oxidative addition reactions. When the nitrogen donor of the pincer ligand is an aza-crown ether macrocycle, cation–macrocycle interactions can be supported, leading to divergent reactivity in some cases. New iridium and rhodium complexes supported by aminophosphinite pincer-crown ether ligands were synthesized. Iridium-catalyzed hydroformylation of allylbenzene was explored. Catalytic amounts of LiOTf (OTf = trifluoromethanesulfonate) doubled the rate of hydrofunctionalization. The iridium pincer complexes were found to undergo remetallation pathways under the conditions of catalysis. This guided the design of a new, more active iridium catalyst supported by a pincer ligand with a methoxy substituent incorporated to prevent remetallation. Rhodium-catalyzed hydroformylation of 1-octene was explored as well. A systematic decrease in the n (linear) to iso (branched) aldehyde ratio was observed in the presence of increasingly bulky ammonium additives. However, catalyst stability studies showed that rhodium pincer complexes undergo decomposition under hydroformylation conditions and presumably simply act as pre-catalysts. The first mononuclear gold(III) PNP pincer complexes (PNP = bis(2- diisopropylphosphinophenyl)amide) are reported. The chloro complex [(PNP)Au(Cl)][OAcF] (OAcF = OCOCF3) was synthesized by microwave irradiation of a tetrachloroaurate salt and the neutral PNHP ligand. Dehalogenation with AgOAcF afforded the trifluoroacetate-bound complex [(PNP)Au(OAcF)][OAcF]. Electronic absorption spectroscopy and time-dependent density functional theory studies assigned the electronic transition that imbues the complexes with a deep royal blue color. The Au(III) trifluoroacetate complex is surprisingly stable, and no reactivity towards ethylene was observed, even under high pressures and at high temperatures. Density functional theory calculations suggest that the lack of reactivity is due to the high energy of the putative dicationic ethylene-bound intermediate invoked in a formal insertion reaction. Spring 2018 2018 Chemistry eng Doctor of Philosophy Dissertation Chemistry Alexander Miller Thesis advisor Thomas Meyer Thesis advisor Gerald Meyer Thesis advisor Frank Leibfarth Thesis advisor Jeffrey Johnson Thesis advisor text University of North Carolina at Chapel Hill Degree granting institution Javier Grajeda Creator Department of Chemistry College of Arts and Sciences PINCER COMPLEXES OF PRECIOUS METALS The synthesis and characterization of several new iridium(I) and iridium(III) carbonyl complexes supported by aminophosphinite pincer ligands is reported. A surprising diversity of reaction pathways were accessible upon treatment of Ir carbonyl complexes with salts of redox-inactive alkali, alkaline earth, and lanthanide metal cations. Iridium(III) hydridocarbonyl chloride complexes underwent either halide abstraction or halide substitution reactions, whereas iridium(I) carbonyl complexes underwent protonative oxidative addition reactions. When the nitrogen donor of the pincer ligand is an aza-crown ether macrocycle, cation–macrocycle interactions can be supported, leading to divergent reactivity in some cases. New iridium and rhodium complexes supported by aminophosphinite pincer-crown ether ligands were synthesized. Iridium-catalyzed hydroformylation of allylbenzene was explored. Catalytic amounts of LiOTf (OTf = trifluoromethanesulfonate) doubled the rate of hydrofunctionalization. The iridium pincer complexes were found to undergo remetallation pathways under the conditions of catalysis. This guided the design of a new, more active iridium catalyst supported by a pincer ligand with a methoxy substituent incorporated to prevent remetallation. Rhodium-catalyzed hydroformylation of 1-octene was explored as well. A systematic decrease in the n (linear) to iso (branched) aldehyde ratio was observed in the presence of increasingly bulky ammonium additives. However, catalyst stability studies showed that rhodium pincer complexes undergo decomposition under hydroformylation conditions and presumably simply act as pre-catalysts. The first mononuclear gold(III) PNP pincer complexes (PNP = bis(2- diisopropylphosphinophenyl)amide) are reported. The chloro complex [(PNP)Au(Cl)][OAcF] (OAcF = OCOCF3) was synthesized by microwave irradiation of a tetrachloroaurate salt and the neutral PNHP ligand. Dehalogenation with AgOAcF afforded the trifluoroacetate-bound complex [(PNP)Au(OAcF)][OAcF]. Electronic absorption spectroscopy and time-dependent density functional theory studies assigned the electronic transition that imbues the complexes with a deep royal blue color. The Au(III) trifluoroacetate complex is surprisingly stable, and no reactivity towards ethylene was observed, even under high pressures and at high temperatures. Density functional theory calculations suggest that the lack of reactivity is due to the high energy of the putative dicationic ethylene-bound intermediate invoked in a formal insertion reaction. Chemistry eng Doctor of Philosophy Dissertation Chemistry Alexander Miller Thesis advisor Thomas Meyer Thesis advisor Gerald Meyer Thesis advisor Frank Leibfarth Thesis advisor Jeffrey Johnson Thesis advisor text University of North Carolina at Chapel Hill Degree granting institution 2018 2018-05 Javier Grajeda Author Department of Chemistry College of Arts and Sciences PINCER COMPLEXES OF PRECIOUS METALS The synthesis and characterization of several new iridium(I) and iridium(III) carbonyl complexes supported by aminophosphinite pincer ligands is reported. A surprising diversity of reaction pathways were accessible upon treatment of Ir carbonyl complexes with salts of redox-inactive alkali, alkaline earth, and lanthanide metal cations. Iridium(III) hydridocarbonyl chloride complexes underwent either halide abstraction or halide substitution reactions, whereas iridium(I) carbonyl complexes underwent protonative oxidative addition reactions. When the nitrogen donor of the pincer ligand is an aza-crown ether macrocycle, cation–macrocycle interactions can be supported, leading to divergent reactivity in some cases. New iridium and rhodium complexes supported by aminophosphinite pincer-crown ether ligands were synthesized. Iridium-catalyzed hydroformylation of allylbenzene was explored. Catalytic amounts of LiOTf (OTf = trifluoromethanesulfonate) doubled the rate of hydrofunctionalization. The iridium pincer complexes were found to undergo remetallation pathways under the conditions of catalysis. This guided the design of a new, more active iridium catalyst supported by a pincer ligand with a methoxy substituent incorporated to prevent remetallation. Rhodium-catalyzed hydroformylation of 1-octene was explored as well. A systematic decrease in the n (linear) to iso (branched) aldehyde ratio was observed in the presence of increasingly bulky ammonium additives. However, catalyst stability studies showed that rhodium pincer complexes undergo decomposition under hydroformylation conditions and presumably simply act as pre-catalysts. The first mononuclear gold(III) PNP pincer complexes (PNP = bis(2- diisopropylphosphinophenyl)amide) are reported. The chloro complex [(PNP)Au(Cl)][OAcF] (OAcF = OCOCF3) was synthesized by microwave irradiation of a tetrachloroaurate salt and the neutral PNHP ligand. Dehalogenation with AgOAcF afforded the trifluoroacetate-bound complex [(PNP)Au(OAcF)][OAcF]. Electronic absorption spectroscopy and time-dependent density functional theory studies assigned the electronic transition that imbues the complexes with a deep royal blue color. The Au(III) trifluoroacetate complex is surprisingly stable, and no reactivity towards ethylene was observed, even under high pressures and at high temperatures. Density functional theory calculations suggest that the lack of reactivity is due to the high energy of the putative dicationic ethylene-bound intermediate invoked in a formal insertion reaction. Spring 2018 2018 Chemistry eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry Alexander Miller Thesis advisor Thomas Meyer Thesis advisor Gerald Meyer Thesis advisor Frank Leibfarth Thesis advisor Jeffrey Johnson Thesis advisor text Javier Grajeda Creator Department of Chemistry College of Arts and Sciences The synthesis and characterization of several new iridium(I) and iridium(III) carbonyl complexes supported by aminophosphinite pincer ligands is reported. A surprising diversity of reaction pathways were accessible upon treatment of Ir carbonyl complexes with salts of redox-inactive alkali, alkaline earth, and lanthanide metal cations. Iridium(III) hydridocarbonyl chloride complexes underwent either halide abstraction or halide substitution reactions, whereas iridium(I) carbonyl complexes underwent protonative oxidative addition reactions. When the nitrogen donor of the pincer ligand is an aza-crown ether macrocycle, cation–macrocycle interactions can be supported, leading to divergent reactivity in some cases. New iridium and rhodium complexes supported by aminophosphinite pincer-crown ether ligands were synthesized. Iridium-catalyzed hydroformylation of allylbenzene was explored. Catalytic amounts of LiOTf (OTf = trifluoromethanesulfonate) doubled the rate of hydrofunctionalization. The iridium pincer complexes were found to undergo remetallation pathways under the conditions of catalysis. This guided the design of a new, more active iridium catalyst supported by a pincer ligand with a methoxy substituent incorporated to prevent remetallation. Rhodium-catalyzed hydroformylation of 1-octene was explored as well. A systematic decrease in the n (linear) to iso (branched) aldehyde ratio was observed in the presence of increasingly bulky ammonium additives. However, catalyst stability studies showed that rhodium pincer complexes undergo decomposition under hydroformylation conditions and presumably simply act as pre-catalysts. The first mononuclear gold(III) PNP pincer complexes (PNP = bis(2- diisopropylphosphinophenyl)amide) are reported. The chloro complex [(PNP)Au(Cl)][OAcF] (OAcF = OCOCF3) was synthesized by microwave irradiation of a tetrachloroaurate salt and the neutral PNHP ligand. Dehalogenation with AgOAcF afforded the trifluoroacetate-bound complex [(PNP)Au(OAcF)][OAcF]. Electronic absorption spectroscopy and time-dependent density functional theory studies assigned the electronic transition that imbues the complexes with a deep royal blue color. The Au(III) trifluoroacetate complex is surprisingly stable, and no reactivity towards ethylene was observed, even under high pressures and at high temperatures. Density functional theory calculations suggest that the lack of reactivity is due to the high energy of the putative dicationic ethylene-bound intermediate invoked in a formal insertion reaction. 2018-05 2018 Chemistry eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Alexander Miller Thesis advisor Thomas Meyer Thesis advisor Gerald Meyer Thesis advisor Frank Leibfarth Thesis advisor Jeffrey Johnson Thesis advisor text Grajeda_unc_0153D_17936.pdf uuid:aa26fd88-e705-486b-a407-ad3015991cbd 2020-06-13T00:00:00 2018-06-06T16:39:06Z proquest application/pdf 8802963