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FRESH Lecture: Computational Studies of Reactivity and Kinetics in Homogeneous Catalysis: Challenges and Perspectives

Thursday 11 October 2018
Gorlaeus Building
Einsteinweg 55
2333 CC Leiden


Reaction mechanisms are often of great interest in catalysis, as they offer some of the insight needed in order to develop improved catalysts or conditions – thereby also providing a means to make transformations more sustainable. Characterizing reaction kinetics as well as the mechanism is even more valuable. Accordingly, computational chemistry has long sought to address reaction mechanisms. Qualitatively, ab initio or density functional theory (DFT) electronic structure methods are well known to be able to characterize mechanisms in a valuable way, e.g. by identifying the structure of elusive intermediates or of transition states. Quantitative predictions of mechanisms, in the sense of using computation to calculate reaction kinetics, is more elusive.

In this talk, I will discuss recent progress and challenges in this area emerging from both published [1,2] and unpublished work in my group concerning this problem. For the published work, I will address two examples: cobalt-catalyzed hydroformylation [1], where using accurate explicitly-correlated coupled-cluster methods allows use to obtain near-quantitative models of catalysis, and the organocatalytic Morita-Baylis-Hillmann reaction [2] which remains considerably more challenging. I will also talk about the mechanisms involved in iron-catalyzed oxidation [3].


  1. (a) L. E. Rush, P. G. Pringle and J. N. Harvey, “Computational Kinetics of Cobalt-Catalyzed Alkene Hydroformylation”, Angew. Chem., Int. Ed., 53 (2014) 8672. (b) E. N. Szlapa and J. N. Harvey, “Computational Modelling of Selectivity in Cobalt-Catalyzed Propene Hydroformylation”, Chem. Eur. J. (2018) in press, see DOI.
  2. Z. Liu, C. Patel, J. N. Harvey and R. B. Sunoj, “Mechanism and reactivity in the Morita–Baylis– Hillman reaction: the challenge of accurate computations”, Phys. Chem., Chem. Phys. 19 (2017) 30647.
  3. M. Feldt, Q. M. Phung, K. Pierloot, R. A. Mata, and J. N. Harvey, “On the Limits of Coupled Cluster Calculations for Non-Heme Iron Complexes”, to be submitted
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