A Career in Catalysis: Odile Eisenstein

Abstract

On the occasion of Professor Odile Eisenstein's 70th birthday and her stepping down as Associate Editor of ACS Catalysis, we reflect on and highlight her distinguished career in computational chemistry and homogeneous catalysis. In this Account we present selected examples of her early work on the computational understanding of transition metal complexes, the evolution of the field towards the quantitative reproduction of these systems, with a final focus on her specific contributions to important catalytic processes including olefin metathesis, s-bond metathesis, and catalytic oxidations.

Experiments and Direct Dynamics Simulations That Probe η2-Arene/Aryl Hydride Equilibria of Tungsten Benzene Complexes

“…Beyond the complexes of benzene (2), anisole (3), and trifluorotoluene (4) already discussed, we surveyed o-hexafluoroxylene ( 5), pyridine-borane (6), naphthalene (7), thiophene (8), and cyclohexene (9). For the o-hexafluoroxylene benzene complex 5, while initially no C-H activated product was observed, over 5 days in benzene-d 6 a new complex is formed in a 1:20 (5H:5) ratio that has resonances consistent with C-H activation (notably a new set of Tp4 protons at 5.76, 5.70, and 5.31 ppm) along with a resonance at 9.30 ppm with J PH = 98 Hz and J WP = 31 Hz) that grows in over time.…”

“…[1][2][3][4] For those methods employing π-basic transition-metal catalysts, the key step often involves the insertion of the metal (i.e., oxidative addition), and numerous studies have been carried out on systems that model this process. [5][6][7][8][9][10][11] For aromatic molecules, chemoselectivity is a critical issue, not only between sp 2 vs sp 3 (e.g., benzylic) carbons but also between different positions within the aromatic ring. The latter is determined by both thermodynamic and kinetic factors, not only for insertion but also for the binding and migration events that precede it (Scheme 1).…”

From the Felkin‐Anh Rule to the Grignard Reaction: an Almost Circular 50 Year Adventure in the World of Molecular Structures and Reaction Mechanisms with Computational Chemistry**

“…article published in ACS Catalysis in 2019, with the flattering title of A Career in Catalysis: Odile Eisenstein. [1] Five former co-workers who became colleagues and friends, David Balcells, Eric Clot, Stuart A. Macgregor, Feliu Maseras and Lionel Perrin, joined efforts to write this glowing description of my scientific activities in the domain of organometallic chemistry and the relevance to homogeneous catalysis. There is no need to repeat what is so well described in this publication, which I recommend to interested readers.…”

“…It is a Jahn Teller unstable structure that distorts toward a square based pyramid or a Y structure. For an orbital correlation diagram of these distortions see reference [50] and a summary in reference [1].…”

“…We determined that lanthanide hydrides react with simple molecules like H 2 , CH 4 , SiH 4 , CF 4 by σ-bond metathesis mechanism. Lionel Perrin gives a nice summary of our studies in reference [1].…”