In this literature discussion, students read an Inorganic Chemistry paper (doi: 10.1021/ic503062w) about diarylamido-based PNZ pincer ligands and their Ni, Pd, and Rh complexes. Specifically, this paper uses IR and E1/2 potentials to demonstrate that the redox events occur not on the metal center but on the pincer ligands. For these non-innocent ligands, the electron donating ability of the pincer ligand towards the metal is more strongly influenced by the donors directly attached to the metal (phosphorus or nitrogen substituents) while the oxidation potential is more affected by the substituents on the diarylamine backbone. This paper also provides x-ray crystallography data, NMR spectra (including J-coupling information), and a wealth of synthetic information. This LO was created for the 2016 TUES Viper Workshop on organometallic chemistry.
In answering these questions, a student will…
● Employ textual clues to define chemical terms such as pincer ligands
● Apply CBC rules to count electrons for pincer-ligand containing complexes
● Relate v(CO) stretching frequencies to electron donating abilities of ligands
● Integrate prior knowledge of periodic trends and electrochemical data from the paper to refine their definition of non-innocent ligands.
● Correlate electrochemical potential to the “electron richness” of the complex
Students should read the paper and complete the reading guide before the literature discussion.
We hope that instructors will mix and match questions that are appropriate to their classes. In particular, instructors may want to be selective among the in-depth questions 5-19 depending on the desired emphasis.
Questions 1-4 assess scientific reading competency and foundational concepts, question 5-11 address fundamental inorganic topics related to changing electron density on the metal, wheras questions 12-19 require deeper discussion of ligand non-innocence and experimental methods to determine difference in electron richness.
Note: we envision question 4 being divided up among multiple groups with each group getting one of the rows. Then, the instructor should highlight the fact that all complexes had the same values.