Solvation Science Student Challenge (S3C)

A variety of exciting and useful sources and background information on the topic and tracks can be found in the following.

General Information

This key publication provides more information on the background of the challenge:

D. Koley, S. De, N. Sivendran, L. J. Gooßen, Isomerization of functionalized olefins using the dinuclear catalyst [PdI(μ-Br)(PtBu3)]2: A mechanistic study, Chem. Eur. J. (2021),  DOI:10.1002/chem.202102554

This is the original literature on transition state theory:

• H. Eyring, The Activated Complex in Chemical Reactions, J. Chem. Phys. (1935), 3, 107 – 115.

The Energetic Span Model is described in the following publications:

• S. Kozuch, S. Shaik, How to Conceptualize Catalytic Cycles? The Energetic Span Model, Acc. Chem. Res. (2011), 44, 101 -110
• S. Kozuch, A refinement of everyday thinking: the energetic span model for kinetic assessment of catalytic cycles, Wiley Interdiscip. Rev. Comput. Mol. Sci. (2012), 2, 795–815

Reactions with this unusual energy profile, in which the selectivity-determining step is lower as the preceding rate-determining step, were also discussed and analyzed In the context of kinetic isotope effects:

• E. M. Simmons, J. F. Hartwig, On the Interpretation of Deuterium Kinetic Isotope Effects in C-H Bond Functionalizations by Transition-Metal Complexes, Angew. Chem. Int. Ed. (2012) 51, 3066 – 3072

Regarding solvent dependencies on the observed kinetic isotope effect in solvolysis experiments, it is interesting to look at the following paper:

• V. J. Shiner, R. D. Fisher, W. Dowd, Enhancement of Solvolysis Rates by Wagner-Meerwein Rearrangements of Ion Pairs, J. Am. Chem. Soc. (1969), 91, 7748 – 7749.

Although the reactions differ from the scenario of a stereoselective transformation in the previous two studies, it might be interesting to look into the above mentioned studies from E.M. Simmons and V. J. Shiner and to transfer them to the actual problem.

Helpful information might be also found in literature on biocatalyzed reactions (enzyme-substrate complexes). 

To get a good first introduction to the selectivity prediction problem in organocatalysis in general, it is worth looking at review articles such as:

• J. Sterling, S. Zavitsanou, J. Ford, F. Duarte, Selectivity in organocatalysis – From qualitative to quantitative predictive models, Wiley Interdiscip. Rev. Comput. Mol. Sci. (2021):e1518

Spectroscopy

To get a broad overview in optical spectroscopy methods, the following book can be recommended:

• W. W. Parson, Modern Optical Spectroscopy, Student Edition, Springer-Verlag Berlin Heidelberg, 2009
• B. Heaton, Mechanisms in Homogeneous Catalysis: A Spectroscopic Approach, Wiley-VCH Verlag, 2005

Computing

Following Review Articles and Books might give a good overview on used computational approaches to analyze catalytic cycles and to predict the selctivity of a reaction:

• B. Peters, Reaction Rate Theory and Rare Events Simulations, Elsevier B.V., 2017
• J. N. Harvey, F. Himo, F. Maseras, L. Perrin, Scope and challenge of computational methods for studying mechanism and reactivity in homogeneous catalysis, ACS Catal. (2019), 9, 9803 – 6813.
• P. Vidossich, M. De Vivo, The role of first principles simulations in studying (bio)catalytic processes, Chem Catalysis, (2021), 1, 69–87.
• K. Jorner, A. Tomberg, C. bauer, C. Sköld, P.-O. Norrby, Organic reactivity from mechanism to machine learning, Nat. Reviews , (2021), 5, 240 – 255.