Affiliate Professor of Chemistry
Director, Center for Enabling New Technologies through Catalysis
Ph.D. University of California at Berkeley, 1988
(Organometallic and Inorganic Chemistry)
One of the most important applications of organometallic chemistry has been the use of organotransition metal catalysts in the commercial production of chemicals, pharmaceuticals and organic materials. The reaction steps in the catalytic cycles are typically general, or so called fundamental reactions in organometallic chemistry, such as oxidative addition, reductive elimination, migratory insertion and beta-hydride elimination. Understanding the mechanisms of these basic reaction steps is key to the improvement of current catalysts and to the design of new catalytic systems. The Goldberg group focuses on developing detailed mechanistic understanding of these fundamental reactions with the goal of creating catalysts for desirable and challenging transformations.
As an example, in one particular project in the group, the reaction steps that could be involved in the selective oxidation of alkanes to alcohols are being studied. Shown below is an idealized catalytic cycle for converting methane to methanol – oxidative addition of the C-H bond forms a metal alkyl hydride, insertion of oxygen into the metal hydride bond forms a metal alkyl hydroxide species, and finally C-O reductive elimination forms the alcohol product and regenerates the catalyst. Understanding how each step proceeds, what type of MLn fragment (geometry and ligand set) is needed, and what type of solvent system will promote that reaction step provides insight and direction to efforts to rationally design catalysts that will carry out such transformations. Some other transformations for which we are trying to develop catalysts are anti-Markovnikov hydration and hydroamination of olefins, oxidation of olefins with molecular oxygen and the release of hydrogen from amine boranes and other viable hydrogen storage materials.
Ph.D. students working on projects in the Goldberg group are trained in synthesis, characterization, and mechanistic analysis using a variety of experimental, spectroscopic and analytical methods. These include the manipulation of air-sensitive compounds by Schlenk and vacuum line techniques, high field multinuclear NMR, IR, and UV-visible spectroscopy, mass spectrometry, and X-ray crystallography.
Denney, M. C.; Pons, V.; Hebden, T. J.; Heinekey, D. M., Goldberg, K. I. “Efficient Catalysis of Ammonia Borane Dehydrogenation.” J. Am. Chem. Soc. 2006, 128, 12048-12049.
Kloek, S. M.; Goldberg, K. I. “Competitive C-H Bond Activation and β-Hydride Elimination at Platinum(II).” J. Am. Chem. Soc. 2007, 129, 3460-3461.
Kloek, S. M.; Heinekey, D. M.; Goldberg, K. I. “C-H Bond Activation by Rhodium(I)Hydroxide and Phenoxide Complexes.” Angew. Chem., Int. Ed. 2007, 46, 4736–4738.
Pawlikowski, A. V.; Getty, A. D. Goldberg, K. I. “Alkyl Carbon-Nitrogen Reductive Elimination from Pt(IV) Sulfonamide Complexes.” J. Am. Chem. Soc. 2007, 129, 10382–10393.
Luedtke, A.; Goldberg, K. I. “Reductive Elimination of Ethane from Five-coordinate Pt(IV) Alkyl Complexes.” Inorg. Chem. 2007, 46, 8696–8698.