A Career in Catalysis: Didier Astruc

Abstract

We are honored to reflect on and highlight in this Account Didier Astruc's achievements in various aspects of catalysis stretching from his concept and design of organoiron electron reservoir complexes and application to redox and electrocatalysis to his dendritic constructions leading to their use in dendritic catalysis, supramolecular nanocatalysis, and energy-related catalysis. It is at the end of the 70s that Didier Astruc isolated the first stable, well-characterized 19-electron sandwich complex as an electron reservoir and disclosed their catalytic applications. At the same time, he developed an original system of arene polyfunctionalization to star-shaped molecules and dendrimers that he then decorated with catalysts for oxidation, electrocatalysis, polymerization by ROMP, and other olefin metathesis reactions. After disclosure by his group of click metallodendrimers during the first decade of this century, he used them as templates for synthesis of well-defined ultrasmall metal nanoparticles extremely active in catalysis for olefin hydrogenation and C–C bond formation using extremely low catalytic amounts. During the last 15 years, Didier Astruc designed dendritic micellar nanoreactors for molecular, ionic, and nanoparticle catalysis; autocatalysis; and nanozyme catalysis. Recently, his interest focused inter alia on nanocatalyzed hydrogen (H2) production with very efficient endo- and exoreceptors and CO2 fixation, a field of sustainable energy in which he and his group are currently very active.

Cobalt‐Catalyzed Bis‐Borylation of Quinolines: The Importance of the Cobalt Triplet State

“…Finally, the 2-methylquinolines, also called quinaldines, work very smoothly in our conditions at room temperature, whereas using Park's rhodium complex required an increase of the temperature. [17] This result proves that the first hydroboration is not sensitive to the steric hindrance, contrary to our previously published hydrosilylation. [12] Thus, quinaldines 1 s, 1 t, 1 u, 1 v, 1 w were selectively converted into the desired products without formation of side-products and borylated tetrahydroquinolines 5 s-5 w were isolated in yield range of a 46-67 %.…”

“…During our investigation Park reported an elegant work based on a similar strategy using a rhodium catalyst with an excess of pinacolborane [17] . Herein we describe a sustainable cascade consisting of a bis‐borylation of quinolines using the simple well‐defined low valent cobalt complex Co‐1 at low temperature in a short reaction time with no excess of pinacol borane.…”

From sandwich complexes to dendrimers: journey toward applications to sensing, molecular electronics, materials science, and biomedicine

“…This detailed mechanistic information disclosed here, confirmed by DFT studies, is also useful for the design of energy-related catalytic devices. [220][221][222][223]…”

First Reusable Catalyst for the Reductive Coupling Reaction of Organohalides with Aldehydes

“…The stability of the produced NPs is increased by their encapsulation within the cavities of the dendrimers. Furthermore, the encapsulation of the NPs prevents their agglomeration and makes it possible to synthesize well-dispersed and small size nanoparticles …”

“…Furthermore, the encapsulation of the NPs prevents their agglomeration and makes it possible to synthesize well-dispersed and small size nanoparticles. 19 In our ongoing attempt to improve a benign catalyzed reaction, 20 recently we have introduced magnetically recyclable Pd−Co bimetallic alloys encapsulated in melamine-based dendrimers (MBD) as a catalyst in the C−C coupling reactions in aqueous media. 17d Our efforts with this catalyst to produce secondary alcohols from the reductive coupling of aryl halides with aldehydes were unsuccessful.…”