This literature discussion is based on a paper by Bill Jones and Frank Feher (J. Am. Chem. Soc., 1986, 108, 4814-4819). In this paper, they study the activation of aromatic C-H bonds by a rhodium complex. Through careful experimental design, they were able to examine isotope effects on the selectivity of the reaction. Analysis of the rate data allowed them to prepare a reaction coordinate free energy diagram. This paper also introduces the effects of C-H bond breaking in early or late transition states on the vibrational energy spacing at both ground and excited states. The paper is a good way to bring kinetic isotope effects into the classroom. The paper also introduces the concept of deuterium labeling experiments and what that information can tell you.

An important aspect of this paper, and what makes it so interesting, is that they are able to get two kinetic isotope effects, one for each step of the reaction. From these two KIEs alone they are able to determine the unexpected rate-determining step of the reaction. It is a triumph of mechanistic investigation into intermediates that are undetectable.

This LO presents a series of guided reading questions that help a student approach and understand the material presented in the paper in a more thorough way. Part one is a guided inquiry that allows the students to derive and understand differing zero point energies for proteated and deuterated compounds. Part two guides students  through the results presented in the paper to help them better understand how experimental data can be used to understand the mechanism of a chemical reaction. There is more to the paper than kinetic isotope effects, but that is the focus I chose while developing it. The LO is suitable for junior or senior undergraduates in an organometallics course or unit within an inorganic course.

I would like to acknowledge Ryan Pakula and Joanne Redford from my Chem 165 course in 2008 who wrote early versions of some of the questions about vibrational states, and a careful critical read by Nancy Williams, who understands this stuff at a much deeper level than I do.

This literature discussion is based on a paper by Karen Goldberg (J. Am. Chem. Soc., 1995, 117, 6889-6896). In this early paper by Goldberg, she studied the reductive elimination of ethane and methyl iodide from dppePtMe3I. The paper is well written, and approachable for undergraduates. It shows a real, interesting application of thermodynamic and kinetic methods to the study of a problem in mechanistic chemistry. The experimental details are complete, and this paper would serve as a good review of kinetics, thermodynamics, and organometallic reaction mechanisms. 


This LO presents a series of guided reading questions that help a student approach some of the material presented in the paper in a more thorough way. It asks students to derive equations and understand how experimental data can be combined into a reaction coordinate free energy diagram. The LO is suitable for junior or senior undergraduates in an organometallics course or unit within an inorganic course.

An update and correction was made to the LO in April 2018. Questions 7 and 8 in the learning object have students address the point of the differing M-C and M-I bonds. For the purposes of understanding what was written at the time, the questions are still valid, but the conclusions drawn in the paper about M-X bond strengths are not. For more information, see the "faculty only" file entitled "Goldberg Update 201804."

This paper is from a Science article from Alan Goldman’s group at Rutgers University. It was one of the literature articles that was assigned during the IONiC VIPEr Workshop in July 2012.  In conjunction with reading the article, workshop participants attended a seminar presented by Alan Goldman on this work.

Here, Goldman’s group showed that C-F bond oxidative addition is possible through an initial C-H bond activation to the (PCP)Ir active complex.  Several key intermediates and Ir complexes were identified using ¹H, ¹³C, ³¹P and ¹⁹F NMR.  LIFDI MS, a soft ionization MS technique, was used to verify the identity of (PCP)Ir(CH₃)F.  DFT calculations along with experimental work were used to elucidate a likely mechanism. 

I teach advanced inorganic chemistry and wanted to find ways to bring in the primary literature, applications, and current research areas.  Students read the article, "Role of Defects in Single-Walled Carbon Nanotube Chemical Sensors" by Eric S. Snow, Nanoletters 2006, 6 (8) pp. 1747 -1751, on their own.  Students are required to answer guided questions (see file Student_questions_Effects of Defects SWCN.doc) and apply basic concepts they have learned in previous courses to understand current literature.  Students learn terminology related to material defects, relate what they learned about defects to material properties, and find other primary literature papers.