Robert Angelici Group

As an Emeritus Professor and Senior Chemist in the Ames Laboratory, Angelici collaborates with other faculty members on two projects:

I. Organometallic Chemistry-Inspired Heterogeneous Catalysis

In collaboration with Professor Keith Woo, we have uncovered reactions that are catalyzed by bulk gold metal. Our studies are grounded in known reactions of organic ligands in organometallic transition metal complexes. Although gold metal has a reputation for being a poor catalyst (except when its particle sizes are < 5 nm), we have found that bulk gold is able to catalyze the following reactions involving oxidations with O2:

A. Isocyanides (C≡N−R) with Amines

Figure 1



B. CO with Primary Amines



C. Oxidative-dehydrogenation of Amines



Gold-catalyzed reactions of diazoalkanes that do not involve O2:



From these early studies, it is obvious that gold metal is not as catalytically inactive as previously assumed. Using principles learned from organometallic chemistry, we will explore other reactions on other metal surfaces. [Published papers giving details of this work are given in the publications list.]

II. Electrochemical Reduction of CO2

With goals of reducing the amount of CO2 in the atmosphere and utilizing excess electric energy produced by wind and solar energy installations during low-electric-demand times, we will explore the electrochemical reduction of CO2 (emitted by power plants) to produce hydrocarbons and other organic molecules that can be used as fuels. This project will be done in collaboration with Professors Andrew Hillier and Keith Woo.


Y. Zhou, B. G. Trewyn, R. J. Angelici and L. K. Woo, “Catalytic Reactions of Carbene Precursors on Bulk Gold Metal,” J. Am. Chem. Soc., 131, 11734-11743 (2009).

J. W. Wiench, C. Michon, A. Ellern, P. Hazendonk, A. Iuga, R. J. Angelici and M. Pruski, “Solid-State NMR Investigations of the Immobilization of a BF4- Salt of a Palladium(II) Complex on Silica,” J. Am. Chem. Soc., 131, 11801-11810 (2009).

R. J. Angelici and M. Lazar, “Isocyanide Ligands Adsorbed on Metal Surfaces:  Applications in Catalysis, Nanochemistry, and Molecular Electronics,” Inorg. Chem., 47, 9155-9165 (2008).

B. Zhu, M. Lazar, B. G. Trewyn and R. J. Angelici, “Aerobic Oxidation of Amines to Imines Catalyzed by Bulk Gold Powder and by Alumina-Supported Gold,” J. Catal., 260, 1-6 (2008).

R. A. Michelin, “Protagonists in Chemistry:  Robert J. Angelici,” Inorg. Chim. Acta, 361, 2991-2996 (2008).

M.-G. Choi, T. C. Ho and R. J. Angelici, “Arene Binding Affinities in [CpRu(h6-arene)]+ Complexes:  Models for the Adsorption of Arenes on Hydrodesulfurization Catalysts,” Organometallics, 27, 1098-1105 (2008).

R. J. Angelici, “Organometallic Chemistry and Catalysis on Gold Metal Surfaces,” J. Organomet. Chem., 693, 847-856 (2008).

Y. Zhou, L. K. Woo and R. J. Angelici, “Solid Acid Catalysis of Tandem Isomerization-Lactonization of Olefinic Acids,” Appl. Catal., A: Gen., 333, 238-244 (2007).

K. M. McWilliams and R. J. Angelici, “Displacement of a cis-Olefin from a trans-Olefin Complex:  CpRu(CO)2(trans-olefin)+,” Organometallics, 26, 5111-5118 (2007).

K. M. McWilliams, A. Ellern and R. J. Angelici, “Synthesis of Cp¢Ru(CO)(L)(h2-olefin)+ Complexes and Kinetic Studies of Olefin Substitution,” Organometallics, 26, 1665-1673 (2007).

M. Lazar, B. Zhu and R. J. Angelici, “Non-Nanogold Catalysis of Reactions of Isocyanides, Secondary Amines, and Oxygen to Give Ureas,” J. Phys. Chem., Sec. C, 111, 4074-4076 (2007).

B. Zhu and R. J. Angelici, “Non-Nanogold Catalyzed Aerobic Oxidation of Secondary Amines to Imines,” Chem. Commun., 2157-2159 (2007).

B. Zhu, A. Ellern, A. Sygula, R. Sygula and R. J. Angelici, “h6-Coordination of the Curved Carbon Surface of Corannulene (C20H10) to (h6-Arene)M2+ (M = Ru, Os),” Organometallics, 26, 1721-1728 (2007).

R. J. Angelici, “Cyaphide (CºP), the Phosphorus Analog of Cyanide (CºN),” Angew. Chem. Int. Ed., 46, 330-332 (2007).

S. A. Stoffregen, P. A. Vecchi, A. Ellern and R. J. Angelici, “A New Approach to the Stabilization of Dibenzothiophene (DBT) Coordination to Metals:  Studies of (h5-C5H4CH2Ph)Ru(CO)2(h1(S)-DBT)+,” Inorg. Chim. Acta, 360, 1711-1716 (2007).

B. Zhu and R. J. Angelici, “Non-Nanogold Catalysis of Carbon Monoxide Oxidative-Amination,” J. Am. Chem. Soc., 128, 14460-14461 (2006).

D. Lazar and R. J. Angelici, “Gold Metal-Catalyzed Reactions of Isocyanides with Primary Amines and Oxygen:  Analogies with Reactions of Isocyanides in Transition Metal Complexes,” J. Am. Chem. Soc., 128, 10613-10620 (2006).

K. J. Stanger and R. J. Angelici, “Silica-Catalyzed tert-Butyl Hydroperoxide Oxidation of Dibenzothiophene and its 4,6-Dimethyl Derivative:  A Route to Low-Sulfur Petroleum Feedstocks,” Energy & Fuels, 20 1757-1760 (2006).

K. J. Stanger, J. W. Wiench, M. Pruski, J. H. Espenson, G. A. Kraus and R. J. Angelici, “Catalytic Oxidation of a Thioether and Dibenzothiophenes Using an Oxorhenium(V) Dithiolate Complex Tethered on Silica,” J. Mol. Catal. A:  Chem., 243, 158-169 (2006).

R. J. Angelici, “Hydrodesulfurization and Hydrodenitrogenation” in Encyclopedia of Inorganic Chemistry; King, R. B., Ed.; 2nd edition; John Wiley & Sons:  New York, 2005; Vol. 3; pp 1860-1877.

P. A. Vecchi, C. M. Alvarez, A. Ellern, R. J. Angelici, A. Sygula, R. Sygula and P. W. Rabideau, “Flattening of a Curved-Surface Buckybowl (Corannulene) by h6-Coordination to {Cp*Ru}+,” Organometallics, 24, 4543-4552 (2005).

P. A. Vecchi, A. Ellern and R. J. Angelici, “Synthetic, Structural and Kinetic Studies of [CpRu(CO)2(m2-h1(S),h6-DBT)RuCp*][PF6]2:  A Dibenzothiophene Bridge between Two Ruthenium Fragments,” Organometallics, 24, 3725-3730 (2005).

J. Chen, V. G. Young, Jr. and R. J. Angelici, “Nucleophilic Addition to the h6-Iridathiabenzene Ligand in [h6-Cp*Ir(C,S-2,5-Me2T)]FeCp+,” Inorg. Chim. Acta, 358, 1623-1634 (2005).