September 2018
Professor Alan S. Goldman
Department of Chemistry and Chemical Biology, Rutgers — The State University of New Jersey
E-mail: alan.goldman@rutgers.edu, Web: http://ccb.rutgers.edu/goldman-alan
Abstract: Iridium complexes have played a leading role in the organometallic chemistry of
alkanes and unreactive C-H bonds since the inception of the field 30 years ago. We have found
that “PCP”-pincer-ligated iridium complexes are particularly effective for the dehydrogenation of
alkanes and have incorporated this reaction into tandem systems for several catalytic
transformations based on dehydrogenation. A closely related class of reactions that we are
exploring is dehydrogenative coupling. More recently we have turned attention to iridium
Phebox complexes. Although the (PCP)Ir and (Phebox)Ir units are formally isoelectronic, the
former operates via C-H activation by Ir(I) while the latter effects dehydrogenation via Ir(III) (as
an acetate complex) and possibly Ir(V) intermediates. Such a high-oxidation-state catalytic cycle
offers advantages for many potential applications of dehydrogenation. In parallel, however, we
find that the low-oxidation-state (+I) chemistry of (Phebox)Ir offers its own novel hydrocarbon
chemistry.
1. Gao, Y.; Guan, C.; Zhou, M.; Kumar, A.; Emge, T. J.; Wright, A. M.; Goldberg, K. I.; Krogh-Jespersen, K.; Goldman, A. S. J. Am. Chem. Soc. 2017,
139, 6338–6350.
2. Wilklow-Marnell, M.; Li, B.; Zhou, T.; Krogh-Jespersen, K.; Brennessel, W. W.; Emge, T. J.; Goldman, A. S.; Jones, W. D. J. Am. Chem. Soc. 2017,
139, 8977–8989.
3. Goldberg, K. I.; Goldman, A. S. Acc. Chem. Res. 2017, 50, 620–626.
4. Kumar, A.; Bhatti, T. M.; Goldman, A. S. Chem. Rev. 2017, 117, 12357–12384.
5. Gao, Y.; Emge, T. J.; Krogh-Jespersen, K.; Goldman, A. S. J. Am. Chem. Soc. 2018, 140, 2260–2264.