About

Karen I. Goldberg is the Vagelos Professor of Energy Research at the University of Pennsylvania. Her professional focus areas include Energy Research, Inorganic Chemistry, and Materials Chemistry. She is based in Room 618 of the VLEST Building and can be contacted via kig@sas.upenn.edu or by phone at 215-573-6756. The information provided highlights her role and research interests within the Department of Chemistry at the University of Pennsylvania but does not include further details about her background or specific contributions.

Research topics

• Chemistry
• Organic chemistry
• Photochemistry
• Physical chemistry
• Inorganic chemistry
• Stereochemistry
• Medicinal chemistry
• Combinatorial chemistry

Selected publications

• Mimicking the Namesake Reaction of Extradiol Catechol Dioxygenase on Iridium

  ChemRxiv · 2026-01-06

  article

  Extradiol catechol dioxygenases expand a benzenediol (catechol) by oxygen atom insertion, generating the corresponding seven-membered oxepinedione. Because the enzymes accept any of the MnII, FeII, or CoII as metallocofactors, each state derived from FeII may have one-electron-shifted analogs. Here, we observe the conversion of a synthetic Ir-peroxo (2) to three complexes – 3, 4, and 5 – models for several previously hypothesized intermediates. An H• can be abstracted from 2 to furnish the metallatrioxolane 3, which is one-electron reduced from the more widely characterized FeII intermediate. Alternatively, photolysis of 2 (467 nm) results in 4, from which an H• can be abstracted to generate 5. Both 4 and 5 are oxepinedione products that remain bound to Ir. The X-ray structure of 5 features a κ2-bound, dianionic ortho ester – a motif which has no prior analogy. These unusual states were made synthetically accessible by incorporating a catechol-like substrate into a multidentate ligand framework.

  PublisherDOI

• Acid Catalyst Is Required for Hydrogenolysis of a Late Metal Hydroxo Complex

  Journal of the American Chemical Society · 2025-12-02

  articleSenior authorCorresponding

  The cationic AuIII pincer complex [(tBuPCP)AuIII–OH]OTf (AuOH, tBuPCP = 2,6-(CH2PtBu2)2C6H3) was prepared and characterized. In contrast to hydrogenolysis reactions of other late metal hydroxides, the hydrogenolysis of AuOH to form the corresponding AuIII–H and water is shown to require an acid catalyst. The kinetic data, collected in acetone-d6, are consistent with a reaction mechanism involving initial protonation to form the AuIII aquo complex, [(tBuPCP)AuIII–OH2](OTf)2 (AuOH2), which was isolated and characterized. Following substitution of the water by a coordinating solvent, the dicationic AuIII center undergoes electrophilic activation of H2 to generate the [(tBuPCP)AuIII–H]OTf product (AuH). The mechanism of hydrogenolysis is supported by experimental and computational (density functional theory) results. A AuIII–dihydrogen complex (Au(H2)) was located along the potential energy surface for the reaction, and computations indicate that deprotonation of Au(H2) by acetone solvent is barrierless. The bonding and properties of the proposed AuIII–H2 complex are consistent with predictions made for high-valent, electrophilic metal–dihydrogen complexes.

  PublisherDOI

• Oxidation of n-alkanes using TS-1 and H2O2: Effects of chain length and solvents

  Applied Catalysis A General · 2025-05-27 · 1 citations

  articleOpen access

  The selective oxidation of n-C 8 H 18 , n-C 12 H 26 , n-C 16 H 34 , n-C 20 H 42 , and n-C 36 H 74 was studied with a goal of using these as models to provide insight into how to functionalize polyolefins. Reactions were carried out using a TS-1 catalyst and H 2 O 2 in a batch reactor with different cosolvents, including methanol, acetone, acetonitrile, methyl ethyl ketone, and methyl butyl ketone. Rates decreased with increasing alkane size, possibly due to the reduced solubility of larger alkanes into the water-rich phases. Cosolvents that promote the partitioning of alkanes in the aqueous phase increased the rates. 1 H NMR spectroscopy demonstrated that ketones were the primary products, although some alcohols also formed. There was preferential reaction at the 2 position in the alkanes, but reaction at central carbons was also observed. The results of this study suggest strategies for using this catalytic chemistry to functionalize polyolefins. • The oxidation of alkanes with varying sizes was investigated using TS-1 and H2O2. • Alkane chain lengths and solvents significantly influence oxidation activity. • Alkane partitioning plays a key role in the reaction. • Oxidation preferentially occurs on the second carbon of alkanes.

  PublisherDOI

• Insertion of Molecular Oxygen into a Gold(III)–Hydride Bond

  Journal of the American Chemical Society · 2024-01-30 · 13 citations

  articleSenior authorCorresponding

  The use of molecular oxygen as an oxidant in chemical synthesis has significant environmental and economic benefits, and it is widely used as such in large-scale industrial processes. However, its adoption in highly selective homogeneous catalytic transformations, particularly to produce oxygenated organics, has been hindered by our limited understanding of the mechanisms by which O2 reacts with transition metals. Of particular relevance are the mechanisms of the reactions of oxygen with late transition metal hydrides as these metal centers are better poised to release oxygenated products. Homogeneous catalysis with gold complexes has markedly increased, and herein we report the synthesis and full characterization of a rare AuIII–H, supported by a diphosphine pincer ligand (tBuPCP = 2,6-bis(di-tert-butylphosphinomethyl)benzene). [(tBuPCP)AuIII–H]+ was found to cleanly react with molecular oxygen to yield a stable AuIII–OOH complex that was also fully characterized. Extensive kinetic studies on the reaction via variable temperature NMR spectroscopy have been completed, and the results are consistent with an autoaccelerating radical chain mechanism. The observed kinetic behavior exhibits similarities to that of previously reported PdII–H and PtIV–H reactions with O2 but is not fully consistent with any known O2 insertion mechanism. As such, this study contributes to the nascent fundamental understanding of the mechanisms of aerobic oxidation of late metal hydrides.

  PublisherDOI

• Bifunctional Ligands: Evaluating the Role of Acidic Protons in the Secondary Coordination Sphere

  Chemistry - A European Journal · 2024-07-15

  articleOpen accessSenior authorCorresponding

  To evaluate bifunctional ligand reactivity involving NH acidic sites in the secondary coordination sphere, complexes where the proton has been substituted with a methyl group (NMe) are often investigated. An alternative strategy involves substitution of the NH group for an O. This contribution considers and compares the merits of these approaches; the synthesis and characterization of cationic square-planar Rh carbonyl complexes bearing diprotic bispyrazole pyridine ligand L1, and the bis-methylated pyrazole pyridine ligand L1Me are described. The syntheses and characterization of the novel monoprotic pyrazole isoxazole pyridine ligand L2 and aprotic bisisoxazole pyridine ligand L3, and their corresponding Rh carbonyl complexes are also described. Comparison of the CO stretching frequencies of the four Rh complexes suggest that substitutions of NH with NMe, as well as with O, lead to significant electronic differences. These electronic differences result in different reactivities with respect to ligand addition/substitution of the Rh carbonyl complexes. Overall, the data suggest that electronic differences arising due to the NH substitutions can be significant and should be considered when the NH group is substituted in investigations of the participation of the NH proton in a reaction.

  PublisherDOI

• Designing Catalysts for Selective Aerobic Oxidations of Hydrocarbons

  WORLD SCIENTIFIC eBooks · 2024-01-01

  book-chapterOpen access1st authorCorresponding
  PublisherDOI

• Lewis Acids and Electron-Withdrawing Ligands Accelerate CO Coordination to Dinuclear Cu^I Compounds

  Inorganic Chemistry · 2023-05-25 · 2 citations

  articleOpen accessCorresponding

  A series of dinuclear molecular copper complexes were prepared and used to model the binding and Lewis acid stabilization of CO in heterogeneous copper CO2 reduction electrocatalysts. Experimental studies (including measurement of rate and equilibrium constants) and electronic structure calculations suggest that the key kinetic barrier for CO binding may be a σ-interaction between CuI and the incoming CO ligand. The rate of CO coordination can be increased upon the addition of Lewis acids or electron-withdrawing substituents on the ligand backbone. Conversely, Keq for CO coordination can be increased by adding electron density to the metal centers of the compound, consistent with stronger π-backbonding. Finally, the electrochemically measured kinetic results were mapped onto an electrochemical zone diagram to illustrate how these system changes enabled access to each zone.

  PublisherOA PDFDOI

• CCDC 2252977: Experimental Crystal Structure Determination

  The Cambridge Structural Database · 2023-05-26

  datasetOpen access

  An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  PublisherDOI

• Ethanol Upgrading to<i>n</i>-Butanol Using Transition-Metal-Incorporated Poly(triazine)imide Frameworks

  ACS Applied Materials & Interfaces · 2023-07-24 · 5 citations

  articleSenior authorCorresponding

  The upgrading of ethanol to n-butanol was performed using a molecular catalyst integrated into a carbon nitride support, one of the first examples of a supported molecular catalyst performing the Guerbet process. Initial studies using crystalline poly(triazine)imide (PTI) with lithium or transition-metal cations imbedded in the support together with a base as the catalyst system did not produce any significant amounts of n-butanol. However, when using the catalyst material formed by treatment of PTI-LiCl with [(Cp*)IrCl2]2 (Cp* = pentamethylcyclopentadienyl) along with sodium hydroxide, a 59% selectivity for butanol (13% yield) was obtained at 145 °C. This PTI-(Cp*)Ir material exhibited distinct UV–vis absorption features and powder X-ray diffractions which differ from those of the parent PTI-LiCl and [(Cp*)IrCl2]2. The PTI-(Cp*)Ir material was found to have a metal loading of 27% iridium per empirical unit of the framework. Along with the formation of n-butanol from the Guerbet reaction, the presence of higher chain alcohols was also observed.

  PublisherDOI

• CCDC 2123869: Experimental Crystal Structure Determination

  The Cambridge Structural Database · 2022-06-20

  datasetOpen accessSenior author

  An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

  PublisherDOI

Recent grants

• Novel Platinum and Palladium Reactions Relevant to Hydrocarbon Functionalization

  NSF · $485k · 2010–2014

• Center for the Activation and Transformation of Strong Bonds (CATSB)

  NSF · $1.5M · 2004–2007

• Organometallic Reactions Relevant to the Functionalization of Alkanes

  NSF · $675k · 2002–2007

• MRI: Acquisition of a 400 MHz Nuclear Magnetic Resonance (NMR) Spectrometer for Chemistry and Energy Research and Education at the University of Pennsylvania

  NSF · $348k · 2018–2021

• Center for Enabling New Technologies through Catalysis

  NSF · $15.6M · 2007–2013

Frequent coauthors

• Werner Kaminsky

  University of Washington

  160 shared

• D. Michael Heinekey

  University of Washington

  98 shared

• Richard A. Kemp

  Iowa State University

  91 shared

• D.X. West

  70 shared

• Michael R. Gau

  40 shared

• Kyle A. Grice

  Belden (United States)

  36 shared

• D.R. Kelman

  33 shared

• K.A. Claborn

  30 shared

Awards & honors

• Raymon E. and Rosellen M. Lawton Distinguished Scholar in Ch…
• Nicole A. Boand Endowed Professor of Chemistry (2010)
• Director of the Center for Enabling New Technologies through…
• Inaugural Director of the Vagelos Institute of Energy Scienc…