Metal carbonyls are the most widely studied organometallic complexes. This exercise uses Gaussian with the GaussView interface to investigate the role of the metal centers on backbonding to the CO ligand. Density Functional Theory (DFT) methods were used to evaluate two classic metal pentacarbonyls, namely Fe(CO)5 and Ru(CO)5.
This is an in-class exercise for upper level inorganic students designed to highlight aspects of symmetry, group theory, MO theory, and Hückel theory. The exercise is an expansion of a Problem Set question I give to my Advanced Inorganic Chemistry class. In this activity, students will develop the MO diagram for the π system of the pentalene dianion using the Hückel approach. They will then consider the effect of folding the ring system using a Walsh diagram.
This is a literature-based activity that focuses on a review I recently published as part of a thematic series on C-H activation.
The review highlights similarities between the newly discovered frustrated Lewis pairs and polarized metal-ligand multiple bonds. There are many ways to use the review, but the attached set of questions focuses on drawing analogies among seemingly diverse types of reactivity using frontier-molecular-orbital considerations.
This contains three parts: A "Pre-Read" section for students to read before coming to class, an in-class worksheet to be worked in groups, and instructor keys for the worksheet.
The purpose of this exercise is to familiarize and give practice with identifying major classes of reaction (oxidative addition, etc.) in an organometallic catalytic cycle. After this exercise, students should be able to do the same for a new catalytic cycle provided by the instructor on a homework set or exam.
This is a literature discussion based on an interesting Bergman/Arnold paper utilizing d2 niobium imido complexes for the semihydrogenation of arylalkynes to Z-alkenes. The mechanism is quite unusual, and I found it to be an interesting paper to discuss after we had talked about the classical hydrogenation mechanisms (typically observed for late transition metals). The students should come into the discussion understanding fundamental reaction mechanisms (including σ-bond metathesis), and it's helpful if they are somewhat familiar with mono- and dihydride mech
This in-class activity and the related problem set allows students to discover the linear and bent bonding modes of NO to metals based on VSEPR theory through guided inquiry. Two examples follow which illustrate how the electrons are counted in NO complexes depending on the coordination mode/formal charge of NO. Students must have had prior practice in counting electrons of complexes to complete the problems.
This in-class activity introduces students to copper-mediated cross coupling reactions. In the literature, many cross coupling reactions are often discussed using palladium as a catalyst, not copper. In my laboratory, we are synthesizing 7-azaindole-based ligands for the development of potential anti-tumor platinum(II) complexes. In addition, I use one of my own publications to demonstrate an application of this synthetic strategy. The students calculate the actual turnover number (TON) and turnover frequency (TOF) for the copper catalyst.
This literature review covers a paper by the Brookhart group in which they describe a very interesting catalytic route for reducing alkyl halides. The paper describes the catalytic mechanism in great detail and shows an unexpected trend in relative reactivities (Br > Cl > I and primary > secondary). One of the primary benefits for using this paper is that it can enable your students to rationalize a mechanism consistent with many different data sets.
This is intended as a guided reading assignment for the JACS Communication, “Mechanism for the Activation of Carbon Monoxide via Oxorhenium Complexes” by Smeltz, Boyle, and Ison; J. Am. Chem. Soc. 2011, 133, 13288-13291. This article will expose students to newly published research and novel reaction mechanisms. It will require students to apply their knowledge of electron counting and organometallic mechanisms.
A detailed in-class analysis of the paper “Mechanism for the Activation of Carbon Monoxide via Oxorhenium Complexes” by Smeltz, Boyle, and Ison; J. Am. Chem. Soc. 2011, 133, 13288-13291. Students will apply their knowledge of organometallic chemistry concepts to the mechanistic scheme in the paper.