Porphyrinoid Chemistry

Our research group is developing new porphyrinoid compounds for applications in biological, catalytic, and environmental chemistry. The synthesis of new expanded or contracted porphyrinoid compounds has attracted the attention of many researchers in organic and inorganic chemistry. In our lab, we have developed a new class of ring-contracted porphyrinoid compounds that we call ‘corrolazines’. These molecules maintain the tetrapyrrolic, macrocyclic structure of porphyrins, but are “contracted” in that they are missing one bridging, meso atom. These molecules also carry a 3- charge when fully deprotonated, which helps to stabilize metal ions in high oxidation states.

Ongoing investigations in our metallocorrolazine chemistry include the study of these molecules in biologically relevant oxidations such as oxygen atom transfer and hydrogen-atom abstraction chemistry. These transformations are of fundamental interest because of their importance in synthesis (e.g. organic synthesis, pharmaceuticals, commodity chemicals), as well as in their roles in heme enzyme function, such as the functioning of cytochrome P-450.

Some highlights of our work in this area include the synthesis of a rare example of an isolable manganese(V)-oxo porphyrinoid compound, the discovery of a new mechanism for high-valent porphyrinoid oxidations involving ArIO oxidants, characterization of the physicochemical properties (XANES/EXAFS, spectroelectrochemistry, HFEPR) of Mn(III) and Mn(V)-oxo corrolazines, elucidation of the hydrogen atom abstraction reactivity of an Mn(V)(O) complex which has relevance to thiolate-ligated heme enzymes (e.g. Cytochrome P450), structural characterization of a rare example of an Mn(V)-imido complex, and the generation and reactivity of a high-valent iron-oxo corrolazine complex.

Selected Publications

McGown, A. J., Badiei, Y. M., Leeladee, P., Prokop, K. A., DeBeer, S., Goldberg, D. P., Synthesis and Reactivity of High-Valent Transition Metal Corroles and Corrolazines. In Handbook of Porphyrin Science, Kadish, K. M.; Smith, K. M.; Guilard, R., World Scientific: New Jersey, 2010; Vol 14, Accepted.

Preparation, Size Control, Surface Deposition, and Catalytic Reactivity of Hydrophobic Corrolazine Nanoparticles in an Aqueous Environment
Cho, K.; Kerber, W. D.; Lee, S. R.; Wan, A.; Batteas, J. D.; Goldberg, D. P.; Inorg. Chem. 2010, 49, 8465- 8473.

Epoxidation Catalyzed by Manganese(V) Oxo and Imido Complexes: Role of the Oxidant-Mn-Oxo (Imido) Intermediate
Leeladee, P.; Goldberg, D. P.; Inorg. Chem. 2010, 49, 3083- 3085.

Unprecedented Rate Enhancements of Hydrogen-Atom Transfer to a Manganese(V)-Oxo Corrolazine Complex
Prokop, K. A.; Visser, S. P.; Goldberg, D. P.; Angew. Chem., Int. Ed. 2010, 49, 5091-5095

Catalytic Reactivity of a Meso-N-Substituted Corrole and Evidence for a High-Valent Iron-Oxo Species
McGown, A. J.; Kerber, W.D.; Fujii, H.; Goldberg, D.P.; J. Am. Chem. Soc. 2009, 131, 8040-8048.

Corrolazines: New Frontiers in High-Valent Metalloporphyrinoid Stability and Reactivity
Goldberg, D.P.; Acc. Chem. Res. 2007, 40, 626-634.

H202 Oxidations Catalyzed by an Iron(III) Corrolazine: Avoiding High-Valent Iron-Oxido Species?
Kerber, W. D.; Ramdhanie, B.; Goldberg, D.P.; Angew. Chem., Int. Ed. 2007, 46, 3718-3721.

Inverse Axial-Ligand Effects in the Activation of H2O2 and ROOH by a Mn(III) Corrolazine
Lansky, D.E.; Sarjeant, A.; Goldberg, D.P.; Angew. Chem. 2006, 45, 8214-8217.

An Isolable, Nonreducible High-Valent Manganese(V) Imido Corrolazine Complex
Lansky, D.E.; Kosack, J.R.; Sarjeant, A.; Goldberg, D.P.; Inorg. Chem. 2006, 45, 8477-8479.

Hydrogen Atom Abstraction by a High-Valent Manganse(V)-Oxo Corrolazine
Lansky, D.E.; Goldberg, D.P.; Inorg. Chem. 2006, 45, 5119-5125.

High-Valent Transition Metal Corrolazines
Kerber, W. D.; Goldberg, D.P.; J. Inorg. Biochem. 2006, 100, 838-857.

Synthesis, Characterization, and Physiochemical Properties of Manganese(III) and Manganese(V)-Oxo Corrolazines
Lansky, D.E.; Mandimutsira, B.; Ramdhanie, B.; Clausen, M.; Penner-Hahn, J.; Zvyagin, S.A.; Telser, J.; Krzystek, J.; Zhan, R.; Zhongping, O.; Kadish*, K.M.; Zhakarov, L.; Rheingold, A.L.; Goldberg, D.P.; Inorg. Chem., 2005, 44, 4485-4498.

Recent Advances in the Chemistry of Corroles and Core-Modified Corroles
Gryko, D.T.; Fox, J.P.; Goldberg, D.P.; J. Porphyrins Phthalocyanines, 2004, 8, 1091-1105.

Catalytic Sulfoxidation and Epoxidation with a Mn(III) Triazacorrole: Evidence for A "Third Oxidant" in High-Valent Porphyrinoid Oxidations
Wang, S. H.; Mandimutsira, B. S.; Todd, R.; Ramdhanie, B.; Fox, J. P.; Goldberg, D. P.; J. Am. Chem. Soc.,2004, 126, 18-19.

Copper(III) and Vanadium(IV)-Oxo Corrolazines
Fox, J. P.; Ramdhanie, B.; Zareba, A. A.; Czernuszewicz, R. S.; Goldberg, D. P.; Inorg. Chem., 2004, 43, 6600-6608.

An Example of O2 Binding in a Cobalt(II) Corrole System and High-Valent Cobalt-Cyano and Cobalt-Alkynyl Complexes
Ramdhanie, B.; Telser, J.; Caneschi, A.; Zakharov, L. N.; Rheingold, A. L.; Goldberg, D. P.; J. Am. Chem. Soc., 2004, 126, 2515-2525.

Octalkoxy-Substituted Phosphorus(V)Triazatetrabenzcorroles via Ring Contraction of Phthalocyanine Precursors
Fox, J. P.; Goldberg, D. P.; Inorg. Chem., 2003, 42, 8181-8191.

A Stable Manganese(V)-Oxo Corrolazine Complex
Mandimutsira, B. S.; Ramdhanie, B.; Todd, R. C.; Wang, H.; Zareba, A. A.; Czernuszewicz, R. S.; Goldberg, D. P.; J. Am. Chem. Soc., 2002, 124, 15170-15171.

Synthesis, Structures, and Properties of a Series of Four-, Five-, and Six-Coordinate Cobalt(III) Triazacorrole Complexes: The First Examples of Transition Metal Corrolazines
Ramdhanie, B.; Zakharov, L. N.; Rheingold, A. L.; Goldberg, D. P.; Inorg. Chem., 2002,41, 4105-4107.

Synthesis of the First Corrolazine: A New Member of the Porphyrinoid Family
Ramdhanie, B.; Stern, C. L.; Goldberg, D. P.; J. Am. Chem. Soc.; 2001,123, 9447-9448.

High-Frequency and –Field Electron Paramagnetic Resonance of High-Spin Manganese(III) in Tetrapyrrole Complexes
Krzystek, J.; Pardi, L. A.; Brunel, L.-C.; Goldberg, D. P.; Hoffman, B. M.; Licoccia, S.; Telser, J.; Spectrochim. Acta, Pt. A, 2002, 1113-1127.

High-Frequency and –Field Electron Paramagnetic Resonance of High-Spin Manganese(III) in Porphyrinic Complexes
Krzystek, J.; Telser, J.; Pardi, L. A.; Goldberg, D. P.; Hoffman, B. M.; Inorg. Chem., 1999, 6121-6129.

Solitaire and Gemini Porphyrazines
Michel, S. L. J.; Goldberg, D. P.; Stern, C.; Barrett, A. G. M.; Hoffman, B. M.; J. Am. Chem. Soc., 2001, 123, 4741-4748.

Metal Ion Binding to Octakis(dimethylamino)porphyrazine: Core Coordination of Mn(III) and Peripheral Coordination of Pd(II)
Goldberg, D. P.; Montalban, A. G.; White A. J. P.; Williams, D. J.; Barrett A. G. M.; Hoffman, B. M.; Inorg. Chem., 1998, 2873-2879.

Molybdocene Porphyrazines: A Peripheral Dithiolene Metallacycle Fused to a Porphyrinic Core
Goldberg, D. P.; Michel, S. L. J.; White, A. J. P.; Williams, D. J.; Barrett, A. G. M.; Hoffman, B. M.; Inorg. Chem., 1998, 2100-2101.

EPR Spectra from ‘EPR-Silent’ Species: High-Field EPR Spectroscopy of Manganese(III) Porphyrins
Goldberg, D. P.; Telser, J.; Krzystek, J.; Montalban, A. G.; Brunel, L.-C.; Barrett, A. G. M.; Hoffman, B. M.; J. Am. Chem. Soc., 1997, 8722-8723.