This LO is a problem-set-style literature discussion that leads students through a critical analysis of an interesting but flawed paper from the recent chemical literature.  Students use the questions to help them work through the paper prior to class, providing plenty of raw material for an in-class discussion about various aspects of the work from a mechanistic organometallic perspective.  The questions help students critically analyze substrate tables, spectroscopic data, and computational results from DFT.

This Guided Literature Discussion was assigned as a course project, and is the result of work originated by students Stefanie Barnett and Katelyn Yowell.  It is based on the article “Synthesis, Electrochemistry, and Reactivity of Half-Sandwich Ruthenium Complexes Bearing Metallocene-Based Bisphosphines”, Shaw, A.P.; Norton, J.R.; Bucella, D.; Sites, L.A.; Kleinbach, S.S.; Jarem, D.A.; Bocage, K.M.; Nataro, C. Organometallics 2009, 28, 3804-3814.

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.

A literature discussion has been developed for two courses: (i) a more basic set of questions appropriate for a sophomore level course or, possibly, a one semester upper level course that does not spend much time on organometallics, and (ii) an in-depth, in- and out-of-class set of assignments appropriate for an organometallics unit or course. Both sets of questions explore the mechanism of olefin metathesis in first- and second-generation Grubbs catalysts using a variety of spectroscopic kinetic techniques that were presented in the paper Sanford, M. S.; Love, J. A.; Grubbs, R. H. J.

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.