Goldman, Alan
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Phone: | 732-445-5232 |
| E-mail: |  |
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| FAX: | 732-445-5312 | |
| Lab: | 732-445-5882 | |
| Office: | Wright Rieman Labs 180/186 | |
| Mail: | Chemistry & Chemical Biology, 610 Taylor Road, Piscataway, NJ 08854 |
| Education | Links |
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Research Summary
The research conducted in my group is focused on the reactions between transition metal complexes and simple organic molecules, particularly hydrocarbons. Our work generally involves a mechanism-based approach to the development of catalysts.
Catalytic functionalization of C-H bonds
The catalytic functionalization of alkanes and other molecules with normally inert C-H bonds is a scientifically challenging problem that presents great opportunities in terms of economics, environmental benefits, and energy self-sufficiency. Catalysts for both the dehydrogenation and the carbonylation of alkanes have been developed in our group; these were among the first efficient organometallic alkane functionalization catalysts.
Pincer catalysts for alkane dehydrogenation
We reported the first efficient solution-phase catalysts for alkane dehydrogenation that require neither the use of photochemical irradiation nor a sacrificial hydrogen acceptor. These “pincer catalysts” have also been found to catalyze reactions as industrially significant as dehydrogenation of n-alkanes, to give the important alpha-olefin products, or dehydrogenation of polymers to allow entry into a diverse manifold of functionalized polymers. Concomitantly, applications in organic synthesis are being investigated.
Alkane Metathesis and other Tandem Systems for Catalytic Hydrocarbon Transformations
Olefins are ubiquitous as intermediates in the petrochemical, commodity chemical, and pharmaceutical industries. Tandem systems that could effect dehydrogenation of alkanes or alkyl groups, followed by a useful secondary reaction of the resulting olefin, offer potentially powerful routes to various products, while avoiding undesirable secondary reactions that can occur in simple alkane dehydrogenation systems. Under the auspices of “CENTC” (see below) and in collaboration with the group of Maurice Brookhart at UNC, we have developed one such system that effects the metathesis of alkanes. A potential application of this system is in the upgrading of Fischer-Tropsch alkane product mixtures to afford greater yields of C9-C19 n-alkanes, ultimately obtained from feedstocks such as coal or biomass. Known as “FT diesel”, this comprises a transportation fuel that burns cleanly and gives ca. 35% greater mileage per ton CO2 emitted than gasoline.
Hydrocarbylation of olefins
A new target of our research is the “hydrocarbylation” of olefins. Like dehydrogenation, this reaction has an unlimited number of potential applications ranging from natural gas liquefaction and petrochemical conversion to complex organic syntheses.
Computational organometallic catalysis
In addition to experimental approaches, ab initio molecular orbital calculations are conducted in collaboration with Prof. K. Krogh-Jespersen. This work has yielded new perspectives on the most fundamental aspects of organometallic chemistry such as the nature of the metal-CO bond or the process of C-H addition. We now believe that the power of computational chemistry has reached the point where the modification or even the de novo design of catalysts using MO calculations is entirely feasible; efforts in this direction are currently underway.
CENTC
The Center for Enabling New Technologies through Catalysis (CENTC) is the first Center for Chemical Innovation funded by the National Science Foundation. CENTC comprises several catalysis-oriented university and government labs located across the country. Some of the work described above, as well as other projects in our lab, is conducted under the auspices of this center. Much of our research involves collaborations, but CENTC projects will give participating students particular opportunities to interact with other leading catalysis groups.
Awards & Honors
- Camille and Henry Dreyfus Distinguished New Faculty Award, 1987
- Union Carbide Innovation Recognition Award, 1992
- Alfred P. Sloan Fellowship, 1992
- Camille and Henry Dreyfus Teacher-Scholar Fellowship, 1992
Publications
"Cleavage of sp3 C-O Bonds via Oxidative Addition of C-H Bonds" J. Choi, Y. Choliy, X. Zhang, T. J. Emge, K. Krogh-Jespersen and A. S. Goldman J. Am. Chem. Soc. 2009, 131, 15627-15629 (pubs.acs)
"Rational Design and Synthesis of Highly Active Pincer-Iridium Catalysts for Alkane Dehydrogenation" S. Kundu, Y. Choliy, G. Zhuo, R. Ahuja, T. J. Emge, R. Warmuth, M. Brookhart, K. Krogh-Jespersen, and A. S. Goldman, Organometallics, 2009, 28, 5432-5444 (pubs.acs)
"Highly Active and Recyclable Heterogeneous Iridium Pincer Catalysts for Transfer Dehydrogenation of Alkanes" Z. Huang, M. Brookhart, A. S. Goldman, S. Kundu, A. Ray, S. L. Scott, and B. C. Vicente, Adv. Synth. Catal. 2009, 351, 188-206 (wiley.com)
"Evaluation of Molybdenum and Tungsten Metathesis Catalysts for Homogeneous Tandem Alkane Metathesis" B. C. Bailey, R. R. Schrock, S. Kundu, A. S. Goldman, Z. Huang and M. Brookhart, Organometallics 2009, 28, 355-360 (pubs.acs)
"Combined Experimental and Computational Studies on Carbon-Carbon Reductive Elimination from Bis(hydrocarbyl) Complexes of (PCP)Ir" R. Ghosh, T. J. Emge, K. Krogh-Jespersen and A. S. Goldman, J. Am. Chem. Soc. 2008, 130, 11317–11327 (pubs.acs)
"Unusual Structural and Spectroscopic Features of Some PNP-Pincer Complexes of Iron" E. M. Pelczar, T. J. Emge, K. Krogh-Jespersen and A. S. Goldman, Organometallics 2008, 27, 5759–5767 (pubs.acs)
"Catalytic Ring Expansion, Contraction, and Metathesis-Polymerization of Cycloalkanes" R. Ahuja, S. Kundu, A. S. Goldman, M. Brookhart, B. C. Vicente, and S. L. Scott Chem. Commun. 2008, 253-255 (rsc.org)
"Dimerization of Alkynes Promoted by a Pincer-Ligated Iridium Complex. C-C Reductive Elimination Inhibited by Steric Crowding" R. Ghosh, X. Zhang, P. Achord, T. J. Emge, K. Krogh-Jespersen, and A. S. Goldman J. Am. Chem. Soc. 2007, 129, 853-866 (pubs.acs)
"Catalytic Alkane Metathesis by Tandem Alkane-Dehydrogenation–Olefin-Metathesis" A. S. Goldman, A. H. Roy, Z. Huang, R. Ahuja, W. Schinski, and M. Brookhart Science 2006, 312, 257-261 (sciencemag.org)
"Dinitrogen Complexes of Pincer-Ligated Iridium" R. Ghosh, M. Kanzelberger, T. J. Emge, G. S. Hall and A. S. Goldman Organometallics 2006, 25, 5668-5671 (pubs.acs)
"Reaction of nitromethane with an iridium pincer complex. Multiple binding modes of the nitromethanate anion" X. Zhang, T. J. Emge, R. Ghosh, K. Krogh-Jespersen and A. S. Goldman Organometallics 2006, 25, 1303-1309 (pubs.acs)
"Preparation of Olefins by Transition Metal-catalyzed Dehydrogenation" A. S. Goldman and R. Ghosh, in Handbook of C-H Transformations - Applications in Organic Synthesis, G. Dyker, Ed., Wiley-VCH, New York; 2005, pp 616-621.
"Selective Cleavage of the C-C Bonds of Aminoethyl Groups, via a Multistep Pathway, by a Pincer Iridium Complex" X. Zhang, T. J. Emge, R. Ghosh, and A. S. Goldman J. Am. Chem. Soc. 2005, 127, 8250-8251 (pubs.acs)
"Dehydrogenation of aliphatic polyolefins catalyzed by pincer-ligated iridium complexes" A. Ray, K. Zhu, Y. V. Kissin, A. E. Cherian, G. W. Coates and A. S. Goldman Chem. Commun. 2005, 3388-3390 (rsc.org)
"Oxidative Addition of Ammonia to Form a Stable Monomeric Amido Hydride Complex" J. Zhao, A. S. Goldman, J. F. Hartwig Science 2005, 307, 1080-1082 (sciencemag.org)
Activation and Functionalization of C-H Bonds; Goldberg, K. I.; Goldman, A. S., Eds., ACS Symposium Series 885; American Chemical Society: Washington, DC, 2004, Table of Contents with links to chapters.
"C-H Bond Activation by Transition Metals: An Introduction" Goldman, A. S. and Goldberg, K. I. in Activation and Functionalization of C-H Bonds; K. I. Goldberg and A. S. Goldman, Eds. 2004;
ACS Symposium Series 885 (go to Oxford Press/ACS books); 1-44 (pdf of chapter)
"Selective Addition to Iridium of Aryl C-H Bonds Ortho to Coordinating Groups. Not Chelation-Assisted" X. Zhang, M. Kanzelberger, T. J. Emge and A. S. Goldman, J. Am. Chem. Soc. 2004, 126, 13192 -13193 (pubs.acs)
"Highly Effective Pincer-Ligated Iridium Catalysts for Alkane Dehydrogenation. DFT Calculations of Relevant Thermodynamic, Kinetic, and Spectroscopic Properties" K. Zhu, P. D. Achord, X. Zhang, K. Krogh-Jespersen and A. S. Goldman, J. Am. Chem. Soc. 2004, 126, 13044-13053 (pubs.acs)
"Distinct Thermodynamics for the Formation and Cleavage of N-H Bonds in Aniline and Ammonia. Directly-Observed Reductive Elimination of Ammonia from an Isolated Amido Hydride Complex" M. Kanzelberger, X. Zhang, T. J. Emge, A. S. Goldman, J. Zhao, C. Incarvito, J. F. Hartwig, J. Am. Chem. Soc. 2003, 125, 13644-13645 (pubs.acs)
"Novel synthesis of enamines by iridium-catalyzed dehydrogenation of tertiary amines", X. Zhang, A. Fried, S. Knapp and A. S. Goldman, Chem. Comm. 2003, 2060 - 2061 (rsc.org)
"The Mechanism of Alkane Transfer-Dehydrogenation catalyzed by a Pincer-Ligated Iridium Complex" K. B. Renkema, Y. V. Kissin and A. S. Goldman, J. Am. Chem. Soc. 2003, 125, 7770-7771 (pubs.acs)
"On the Mechanism of (PCP)Ir-catalyzed Acceptorless Dehydrogenation of Alkanes: a Combined Computational and Experimental Study" K. Krogh-Jespersen, M. Czerw, N. Summa, K. B. Renkema, P. Achord, and A. S. Goldman, J. Am. Chem. Soc. 2002, 124, 11404-11416 (pubs.acs)
"Combined Computational and Experimental Study of Substituent Effects on the Thermodynamics of H2, CO, Arene, and Alkane Addition to Iridium", K. Krogh-Jespersen, M. Czerw, K. Zhu, B. Singh, M. Kanzelberger, N. Darji, P. Achord, K. B. Renkema, and A. S. Goldman, J. Am. Chem. Soc. 2002, 124, 10797-10809 (pubs.acs)
"Homogeneous Dehydrogenation", Encyclopedia of Catalysis, John Wiley & Sons, 2002 (wiley)