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Full-Text Articles in Chemistry
Dark Iron-Catalyzed Reactions In Acidic And Viscous Aerosol Systems Efficiently Form Secondary Brown Carbon, Hind A. Al-Abadleh, Md Sohel Rana, Wisam Mohammed, Marcelo I. Guzman
Dark Iron-Catalyzed Reactions In Acidic And Viscous Aerosol Systems Efficiently Form Secondary Brown Carbon, Hind A. Al-Abadleh, Md Sohel Rana, Wisam Mohammed, Marcelo I. Guzman
Chemistry Faculty Publications
Iron-driven secondary brown carbon formation reactions from water-soluble organics in cloud droplets and aerosols create insoluble and soluble products of emerging atmospheric importance. This work shows, for the first time, results on dark iron-catalyzed polymerization of catechol forming insoluble black polycatechol particles and colored water-soluble oligomers under conditions characteristic of viscous multicomponent aerosol systems with relatively high ionic strength (I = 1–12 m) and acidic pH (∼2). These systems contain ammonium sulfate (AS)/nitrate (AN) and C3–C5 dicarboxylic acids, namely, malonic, malic, succinic, and glutaric acids. Using dynamic light scattering (DLS) and ultra high pressure liquid chromatography-mass spectrometry (UHPLC-MS), …
Allylic Amination And Carbon–Carbon Double Bond Transposition Catalyzed By Cobalt(Ii) Azodioxide Complexes, Kylin A. Emhoff, Ahmed M.H. Salem, Lakshmi Balaraman, Drew M. Kingery, W. Christropher Boyd
Allylic Amination And Carbon–Carbon Double Bond Transposition Catalyzed By Cobalt(Ii) Azodioxide Complexes, Kylin A. Emhoff, Ahmed M.H. Salem, Lakshmi Balaraman, Drew M. Kingery, W. Christropher Boyd
Chemistry Faculty Publications
The unusual cobalt(II) diphenylazodioxide complex salts [Co(az)4](PF6)2 and [Co(bpy)(az)2](PF6)2 have been shown to catalyze the allylic amination/C–C double bond transposition reaction of 2-methyl-2-pentene with PhNHOH, with a turnover number of about 4. The mechanism is proposed to involve a nitroso-ene-like transfer of a PhNO moiety from the azodioxide ligand to the alkene, followed by reduction of the organic product to yield a cobalt(III) intermediate, which is itself reduced back to cobalt(II) by PhNHOH, regenerating PhNO. Hetero-Diels-Alder trapping experiments suggest that an “off-metal” mechanism, in which PhNO is released from the …
Synthesis And Catalytic Activity Of (3,4-Diphenylcyclopentadienone)Iron Tricarbonyl Compounds In Transfer Hydrogenations And Dehydrogenations, Timothy W. Funk, Andrew R. Mahoney, Rebecca A. Sponenburg, Kathryn P. Zimmerman, Daniel K. Kim, Emily E. Harrison
Synthesis And Catalytic Activity Of (3,4-Diphenylcyclopentadienone)Iron Tricarbonyl Compounds In Transfer Hydrogenations And Dehydrogenations, Timothy W. Funk, Andrew R. Mahoney, Rebecca A. Sponenburg, Kathryn P. Zimmerman, Daniel K. Kim, Emily E. Harrison
Chemistry Faculty Publications
Four (3,4-diphenylcyclopentadienone)iron tricarbonyl compounds were synthesized, and their activities in transfer hydrogenations of carbonyl compounds and transfer dehydrogenations of alcohols were explored and compared to those of the well-established [2,5-(SiMe3)2-3,4-(CH2)4(η4-C4C═O)]Fe(CO)3 (3). A new compound, [2,5-bis(3,5-dimethylphenyl)-3,4-diphenylcyclopentadienone]iron tricarbonyl (7), was the most active catalyst in both transfer hydrogenations and dehydrogenations, and compound 3 was the least active catalyst in transfer hydrogenations. Evidence was found for product inhibition of both 3 and 7 in a transfer dehydrogenation reaction, with the activity of 3 being more heavily affected. A monomeric iron hydride derived from 7 was spectroscopically observed during a …
Electronic Effects In Oxidation Reactions Utilizing Dinuclear Copper Complexes With The Bis[3-(2-Hydroxybenzylideneamino)Phenyl] Sulfone Ligand, Armando M. Guidote Jr, Ronald L. Reyes, Riyo Kashihara, Yasuhiko Kurusu, Yoshihiro Masuyama
Electronic Effects In Oxidation Reactions Utilizing Dinuclear Copper Complexes With The Bis[3-(2-Hydroxybenzylideneamino)Phenyl] Sulfone Ligand, Armando M. Guidote Jr, Ronald L. Reyes, Riyo Kashihara, Yasuhiko Kurusu, Yoshihiro Masuyama
Chemistry Faculty Publications
Copper acetate and the ligands bis[3-(3-tert-butyl-2-hydroxy-5-methoxybenzylideneamino)phenyl] sulfone and bis[3-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)phenyl] sulfone were reacted to form the complexes with 2:1 copper:ligand ratio, Cu2[B(t-Bu) (OMe)BAPS](µ-OCH3)2 (4) and with 2:2 copper:ligand ratio, Cu2[B(t-Bu)2BAPS]2 (5), respectively. Structures of 4 and 5 were determined based on IR, UV-Vis, and FAB-MS data in comparison with previously characterized related copper complexes. The two complexes 4 and 5 were utilized in the oxidation of the substrates 2,4- and 2,6-di-tertbutylphenol (dtbp) at -50C with H2O2 in CH2Cl2. The coupling products are preferred in both cases. For 2,4-dtbp, yields of 4,600% and 7,200% of 3,3’,5,5’-tetra-tert-butyl-2,2’- biphenol were achieved with the use …
Tetrahymena Thermophila And Candida Albicans Group I Intron-Derived Ribozymes Can Catalyze The Trans-Excision-Splicing Reaction, P. Patrick Dotson Ii, Ashley K. Johnson, Stephen M. Testa
Tetrahymena Thermophila And Candida Albicans Group I Intron-Derived Ribozymes Can Catalyze The Trans-Excision-Splicing Reaction, P. Patrick Dotson Ii, Ashley K. Johnson, Stephen M. Testa
Chemistry Faculty Publications
Group I intron-derived ribozymes can catalyze a variety of non-native reactions. For the trans-excision-splicing (TES) reaction, an intron-derived ribozyme from the opportunistic pathogen Pneumocystis carinii catalyzes the excision of a predefined region from within an RNA substrate with subsequent ligation of the flanking regions. To establish TES as a general ribozyme-mediated reaction, intron-derived ribozymes from Tetrahymena thermophila and Candida albicans, which are similar to but not the same as that from Pneumocystis, were investigated for their propensity to catalyze the TES reaction. We now report that the Tetrahymena and Candida ribozymes can catalyze the excision of a …