A5015960594- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Catalytic C–H Functionalization Methods
- Organometallic Complex Synthesis and Catalysis
- Cyclopropane Reaction Mechanisms
- Catalytic Cross-Coupling Reactions
- Catalytic Alkyne Reactions
- Magnetism in coordination complexes
- Inorganic Fluorides and Related Compounds
- Radical Photochemical Reactions
- Fluorine in Organic Chemistry
- Organic Light-Emitting Diodes Research
- Metal complexes synthesis and properties
- Coordination Chemistry and Organometallics
- Oxidative Organic Chemistry Reactions
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Synthesis and Catalytic Reactions
- Metal-Catalyzed Oxygenation Mechanisms
- Porphyrin and Phthalocyanine Chemistry
- Crystallography and molecular interactions
- Lanthanide and Transition Metal Complexes
- Advanced Synthetic Organic Chemistry
- Chemical Synthesis and Reactions
University of Wisconsin–Madison
2019-2023
Georgia Institute of Technology
2017-2023
East Carolina University
2010-2013
N,N-Di(6-phenylpyridin-2-yl)aniline (L1), N,N-di(6-(2,4-difluorophenyl)pyridin-2-yl)aniline (L2), N,N-di(3-(pyridin-2-yl)phenyl)aniline (L3), N,N-di(3-(1H-pyrazol-1-yl)phenyl)aniline (L4), N,N-di(3-(3-methyl-1H-pyrazol-1-yl)phenyl)aniline (L5), and N,N-di(3-(4-methyl-1H-pyrazol-1-yl)phenyl)aniline (L6) undergo cyclometalation to produce two types of tetradentate bis-cyclometalated platinum(II) complexes: C∧N*N∧C platinum complexes 1 2 N∧C*C∧N 3−6, respectively, where an "X∧Y" (X, Y = C or N)...
Visible-light capture activates a thermodynamically inert CoIII -CF3 bond for direct C-H trifluoromethylation of arenes and heteroarenes. New trifluoromethylcobalt(III) complexes supported by redox-active [OCO] pincer ligand were prepared. Coordinating solvents, such as MeCN, afford green, quasi-octahedral [(S OCO)CoIII (CF3 )(MeCN)2 ] (2), but in non-coordinating solvents the complex is red, square pyramidal )(MeCN)] (3). Both are thermally stable, 2 stable light. But exposure 3 to...
A new family of low-coordinate Co complexes supported by three redox-noninnocent tridentate [OCO] pincer-type bis(phenolate) N-heterocyclic carbene (NHC) ligands are described. Combined experimental and computational data suggest that the charge-neutral four-coordinate best formulated as Co(II) centers bound to closed-shell [OCO]2– dianions, general formula [(OCO)CoIIL] (where L is a solvent-derived MeCN or THF). Cyclic voltammograms reveal oxidations accessible at potentials below 1.2 V vs...
The reaction of N,N-diphenyl-2,2′-bipyridin-6-amine (L1) and N,N-diphenyl-6-(1H-pyrazol-1-yl)pyridin-2-amine (L2) with K2PtCl4 produced C*N∧N-coordinated cycloplatinated compounds a five–six fused metallacycle 1a 2a, respectively, which were then converted into their phenylacetylide derivatives 1b 2b, respectively. Similar reactions starting from 2-phenyl-6-(1H-pyrazol-1-yl)pyridine (L3) C∧N∧N-coordinated platinum complexes 3a 3b five–five-fused metallacycle. structures 1a, 1b, 3a,...
Novel mixed-ligand rhodium(II) paddlewheel complexes incorporating tethered axial thioether ligands have been synthesized and characterized. The moiety is essential for high yields the suppression of byproducts in cyclopropanation reactions using an electron-deficient diazoacetate. Crystal structures, UV–vis analysis, cyclic voltammetry experiments shed light on catalytic performance complexes.
A cobalt photocatalyst for direct trifluoromethylation of (hetero)arene C(sp2)-H bonds is described and shown to operate via visible light activation a Co-CF3 intermediate, which functions as combined chromophore organometallic reaction center. Chemical oxidations previously reported (OCO)Co complexes containing redox-active [OCO] pincer ligand afford complex two oxidation states above Co(II). Computational spectroscopic studies are consistent with formulation the product...
A series of chiral bowl-shaped diruthenium(II,III) tetracarboxylate catalysts were prepared and evaluated in asymmetric cyclopropanations with donor/acceptor carbenes derived from aryldiazoacetates. The diruthenium self-assembled to generate C4-symmetric structures an analogous manner their dirhodium counterparts. optimum catalyst was found be Ru2(S-TPPTTL)4·BArF [S-TPPTTL = (S)-2-(1,3-dioxo-4,5,6,7-tetraphenylisoindolin-2-yl)-3,3-dimethylbutanoate, BArF...
By merely changing the solvent, two different cyclometalated platinum complexes resulted from either sp(2) or sp(3) C-H bond activation can be prepared selectively. For example, reaction of L1 with K(2)PtCl(4) in MeCN gave exclusively kinetic product 1a, while AcOH was thermodynamically controlled and produced predominantly 1b.
Among Earth-abundant catalyst systems, iron-carbene intermediates that perform C-C bond forming reactions such as cyclopropanation of olefins and C-H functionalization via carbene insertion are rare. Detailed descriptions the possible electronic structures for bonds imperative to obtain better mechanistic insights enable rational design. Here, we report first square-planar complex (
Abstract Visible‐light capture activates a thermodynamically inert Co III −CF 3 bond for direct C−H trifluoromethylation of arenes and heteroarenes. New trifluoromethylcobalt(III) complexes supported by redox‐active [OCO] pincer ligand were prepared. Coordinating solvents, such as MeCN, afford green, quasi‐octahedral [( S OCO)Co (CF )(MeCN) 2 ] ( ), but in non‐coordinating solvents the complex is red, square pyramidal )(MeCN)] ). Both are thermally stable, stable light. But exposure to...
Chiral monoprotected aminoethyl amine (MPAAM) ligands were recently reported to facilitate enantioselective Pd-catalyzed arylation of strong cyclopropane C(sp3)–H bonds. Herein, we describe detailed experimental and theoretical investigations into the influence MPAAM ligands, L1 L2, as well a thioether (MPAThio) ligand, L3, on reaction kinetics, product enantioselectivity, turnover number. We show an unusual negative nonlinear effect in ligand enantiopurity rate ee that has not been shown...
Abstract Heteroarylzirconocene halides such as (II), generated in situ, are found to be excellent coupling partners reactions with functionalized aryl and heteroaryl halides.