Goldman, Alan

Position: 
Distinguished Professor

Alan Goldman

Phone: 848-445-5232

E-mail: E-mail

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
  • B.A., M.S., Ph.D., Columbia University
  • IBM Postdoctoral Fellow, University of Chicago

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

Pincer.jpgWe 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 Transformation

Alkane1.jpgOlefins 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.

Alkane2.jpgAnother tandem reaction discovered by our CENTC team is alkane aromatization. Remarkably this system converts n-alkanes to aromatics, under relatively mild conditions. This is the first homogeneous system reported for dehydroaromatization, and the first catalytic system of any type that converts higher n-alkanes to aromatics of the same carbon number (e.g. n-dodecane gives C12 n-alkyl aromatics).

C-H bond activation toward reactivity at sites other than the C-H bond

C-H_Bond.jpgOxidative addition and its reverse, reductive elimination, comprise perhaps the most important and distinctive class of reactions of transition metal based catalysts and reagents. While this class of reactions is critical for the catalytic transformations of many types of molecules, until now it appeared inaccessible with sp3-C-F and C-O bonds. Such bonds are of great interest in many contexts, ranging from pharmaceuticals to the conversion of biomass to fuels and chemicals.

Our lab has recently discovered the first example of oxidative addition of sp3-C-F bonds, an outgrowth of recent work on the novel addition of sp3-C-O bonds. Perhaps most interestingly, the reactions are found to proceed via an unprecedented pathway, in which the metal atom initially inserts into a carbon-hydrogen (C-H) bond in the molecule. This unusual pathway must also be operative for the reverse reaction, in which C-F or C-O bonds are formed.

In another surprising reaction we have found that C-H addition of an aromatic (tropone) results in nucleophilic activity at a remote site on that molecule. Oxidative addition of C-H bonds has been assumed to have great potential for the purpose of catalyzing functionalization in which there is an overall cleavage of the C-H bond. The discovery of these reactions highlights the possible applicability of C-H bond addition toward functionalization of various substrates, not necessarily at the site of the C-H bond cleavage.

Hydrocarbylation of olefins

Hydro_Carb.jpgA new target of our research is the “hydrocarbylation” of olefins. Like dehydrogenation, this reaction has a nearly 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.

The Sustainable Fuel Solutions IGERT

IGERT's (Integrative Graduate Education and Research Traineeships) represent the flagship interdisciplinary doctoral training program of the National Science Foundation (NSF).

Our Sustainable Fuel Solutions IGERT brings together over 40 faculty members, with research interests spanning a broad range of fuel science, from a diverse group of graduate programs including Chemistry, Chemical Engineering, Environmental Sciences, and Planning and Public Policy. IGERT Fellowships provide full financial support and offer graduate students many opportunities for exposure to and interaction with students and faculty outside of their own area of specialization. 

Note: Rutgers University is committed to providing a healthy and safe environment for faculty, staff, students, visitors, and volunteers in all sites owned, operated, or controlled by the University. This commitment includes supporting a culture of health and safety across the University. The Department of Environmental Health and Safety implements University policy related to public, occupational, and environmental health and safety and provides a wide range of technical services, leadership and oversight. Principal investigators and academic units maximize laboratory safety by implementing and enforcing Rutgers University safety policies, providing laboratory oversight and offering laboratory-specific training as necessary.


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
  • ACS Catalysis Lectureship Award for the Advancement of Catalytic Science, 2012

Representative Publications

"Acid-catalyzed Oxidative Addition of a C-H Bond to a Square Planar d8 Iridium Complex" J. D. Hackenberg, S. Kundu, T. J. Emge, K. Krogh-Jespersen, A. S. Goldman, J. Am. Chem. Soc. ASAP (pubs.acs)

"Synthesis and Characterization of Carbazolide-based Iridium PNP Pincer Complexes. Mechanistic and Computational Investigation of Alkene Hydrogenation: Evidence for an Ir(III)/Ir(V)/Ir(III) Catalytic Cycle" C. Cheng, B. G. Kim, D. Guironnet, M. Brookhart, C. Guan, D. Y. Wang, A. S. Goldman J. Am. Chem. Soc. 2014, 136, 6672−6683 (pubs.acs)

"Regeneration of an Iridium(III) Complex Active for Alkane Dehydrogenation Using Molecular Oxygen" K. E. Allen, D. M. Heinekey, A. S. Goldman and K. I. Goldberg Organometallics 2014, 33, 1337-1340 (pubs.acs)

"Activation of C-O and C-F Bonds by Pincer-Iridium Complexes" J. Hackenberg, K. Krogh-Jespersen and A. S. Goldman, in Advances in Organometallic Chemistry and Catalysis: The Silver / Gold Jubilee International Conference on Organometallic Chemistry Celebratory Book; Pombeiro, A. J. L., Ed.; John Wiley & Sons: Hoboken, NJ, 2014, 39-58.

"Rational Design of Highly Active “Hybrid” Phosphine-Phosphinite Pincer Iridium Catalysts for Alkane Metathesis" A. Nawara-Hultzsch, J. Hackenberg, B. Punji, C. Supplee, T. Emge, B. Bailey, R. R. Schrock, M. Brookhart, A. S. Goldman ACS Catalysis 2013, 3, 2505-2514 (pubs.acs)

"Olefin Hydroaryloxylation Catalyzed by Pincer-Iridium Complexes" M. C Haibach, C. Guan, D. Y. Wang, B. Li, N. Lease, A. Steffens, K Krogh-Jespersen and A S. Goldman J. Am. Chem. Soc. 2013, 135, 15062-15070 (pubs.acs)

"Catalytic Synthesis of n-Alkyl Arenes through Alkyl Group Cross Metathesis" G. E. Dobereiner. J. Yuan. R. R. Schrock. A. S. Goldman, J. D. Hackenberg J. Am. Chem. Soc. 2013, 135, 12572-12575 (pubs.acs)

"(POP)Rh pincer hydride complexes: unusual reactivity and selectivity in oxidative addition and olefin insertion reactions"  M. C. Haibach, D. Y. Wang, T. J. Emge, K. Krogh-Jespersen and A. S. Goldman Chem. Sci. 2013, 4, 3683-3692 (rsc.org

"Cleavage of Ether, Ester and Tosylate C(sp3)-O Bonds by an Iridium Complex, Initiated by Oxidative Addition of C-H Bonds. Experimental and Computational Studies" S. Kundu, J. Choi, D. Y. Wang, Y. Choliy, T. J. Emge, K. Krogh-Jespersen and A. S. Goldman J. Am. Chem. Soc. 2013, 135, 5127-5143 (pubs.acs)

"Alkane Dehydrogenation by C-H Activation at Ir(III)" K. E. Allen, D. M. Heinekey, A. S. Goldman, K I. Goldberg, Organometallics 2013, 32, 1579-1582 (pubs.acs)

"Olefin Isomerization by Iridium Pincer Catalysts. Experimental Evidence for an eta-3-Allyl Pathway and an Unconventional Mechanism Predicted by DFT Calculations" S. Biswas, Z. Huang, Y. Choliy, D. Y. Wang, M. Brookhart, K. Krogh-Jespersen, A. S. Goldman  J. Am. Chem. Soc. 2012, 134, 13276-13295 (pubs.acs)

"Alkane Dehydrogenation" M. Findlater, J. Choi, A. S. Goldman, and M. Brookhart in Alkane C-H Activation by Single-Site Metal Catalysis; Pérez, P. J., Ed.; Springer: New York, 2012; Catalysis by Metal Complexes, Vol. 38, 113-141. (springer)

"Alkane Metathesis by Tandem Alkane-Dehydrogenation-Olefin-Metathesis Catalysis and Related Chemistry" M. C. Haibach, S. Kundu, M. Brookhart, A. S. Goldman, Acc. Chem. Res. 2012, 45, 947-958. (pubs.acs)

"Theoretical Structure–Reactivity Study of Ethylene Insertion into Nickel–Alkyl Bonds. A Kinetically Significant and Unanticipated Role of trans Influence in Determining Agostic Bond Strengths" F. Hasanayn, P. Achord, P. Braunstein, H. J. Magnier, K. Krogh-Jespersen, and A. S. Goldman Organometallics 2012, 31, 4680-4692 (pubs.acs)

"Preparation of Tungsten-Based Olefin Metathesis Catalysts Supported on Alumina" J. Yuan, E. M. Townsend, R. R. Schrock, A. S. Goldman, P. Müller, and M. K. Takase Adv. Synth. Catal. 2011353, 1985-1992 (wiley.com)

"Net Oxidative Addition of C(sp3)-F Bonds to Iridium via Initial C-H Bond Activation" J. Choi, D. Y. Wang, S. Kundu, Y. Choliy, T. J. Emge, K. Krogh-Jespersen and A. S. Goldman Science 2011, 332, 1545-1548 (sciencemag.org)

"Dehydrogenation and Related Reactions Catalyzed by Iridium Pincer Complexes" J. Choi, A. H. R. MacArthur, M. Brookhart, and A. S. Goldman Chem. Rev. 2011, 111, 1761-1779 (pubs.acs)

"Catalytic dehydroaromatization of n-alkanes by pincer-ligated iridium complexes" R. Ahuja, B. Punji, M. Findlater, C. Supplee, W. Schinski, M. Brookhart, and A. S. Goldman Nature Chem. 2011, 3, 167-171 (nature.com)

"Dehydrogenation of Ketones by Pincer-Ligated Iridium. Formation and Reactivity of Novel Enone Complexes" X. Zhang, D. Y. Wang, T. J. Emge and A. S. Goldman Inorg. Chim. Acta 2011, 369, 253-259 (special issue in honor of Robert Bergman) (sciencedirect.com)

"Ir-Catalyzed Functionalization of C–H Bonds" J. Choi and A. S. Goldman Top. Organomet. Chem. 201134, 139-168 (springerlink.com)

"Reactions of phosphinites with oxide surfaces: a new method for anchoring organic and organometallic complexes" B. C. Vicente, Z. Huang, M. Brookhart, A. S. Goldman, and S. L. Scott, Dalton Trans. 2011, 40, 4268-4274. (rsc.org)

"A Highly Stable Adamantyl-Substituted Pincer-Ligated Iridium Catalyst for Alkane Dehydrogenation" B. Punji, T. J. Emge, and A. S. Goldman, Organometallics201029, 2702-2709 (pubs.acs)

"Organometallic chemistry: Carbon–carbon bonds get a break" (News and Views) A. S. Goldman, Nature, 2010, 435-436 (nature.com)

"Dihydrogen/Dihydride or Tetrahydride? An Experimental and Computational Investigation of Pincer Iridium Polyhydrides" T. J. Hebden, K. I. Goldberg, D. M. Heinekey, X. Zhang, T. J. Emge, A. S. Goldman and K. Krogh-Jespersen Inorg. Chem. 2010, 49, 1733-1742 (pubs.acs)

"Efficient Heterogeneous Dual Catalyst Systems for Alkane Metathesis" Z. Huang, E. Rolfe, E. C. Carson, M. Brookhart, A. S. Goldman, S. H. El-Khalafy, A. H. Roy MacArthur, Adv. Synth. Catal. 2010, 352, 125-135 (wiley.com)

"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)


Research Area(s): 
Inorganic Chemistry
Organic Chemistry