Periodic Reporting for period 3 - DoReMI (Dominating redox mechanisms in iron-mediated C-C bond formations: reactivity, new paradigms and applications)
Reporting period: 2023-07-01 to 2024-12-31
In this project, we aim at developing new and efficient methods for promoting the formation of C-C bonds starting from hydrocarbons as starting material, associated with iron-based catalysts. Since iron is a cheap, abundant and non-toxic metal, such a transformation represents a particularly appealing synthetic way in terms of green chemistry.
However, this strategy faces important challenges, such as the understanding of the reactivity of iron catalysts, especially of compounds displaying a carbon-iron bond, which are commonly met as reactive intermediates in catalytic cycles. The C-Fe bond is particularly elusive, highly reactive, and the corresponding intermediates are usually air- and moisture-sensitive. Moreover, they are often paramagnetic, precluding their characterization and monitoring by classic techniques.
The first goal of this project is thus to unveil the main mechanistic parameters governing the reactivity of such compounds (WP1). In a second time, elementary steps for the activation of inert hydrocarbons by tailor-made iron catalysts is optimized (WP2), and catalytic applications for the C-C bond formations are then envisioned (WP3).
Overall, this project will afford new and sustainable C-C bond formations processes with a low energetic footprint, relying on the use of green and eco-friendly iron-based catalysts.
However, this strategy faces important challenges, such as the understanding of the reactivity of iron catalysts, especially of compounds displaying a carbon-iron bond, which are commonly met as reactive intermediates in catalytic cycles. The C-Fe bond is particularly elusive, highly reactive, and the corresponding intermediates are usually air- and moisture-sensitive. Moreover, they are often paramagnetic, precluding their characterization and monitoring by classic techniques.
The first goal of this project is thus to unveil the main mechanistic parameters governing the reactivity of such compounds (WP1). In a second time, elementary steps for the activation of inert hydrocarbons by tailor-made iron catalysts is optimized (WP2), and catalytic applications for the C-C bond formations are then envisioned (WP3).
Overall, this project will afford new and sustainable C-C bond formations processes with a low energetic footprint, relying on the use of green and eco-friendly iron-based catalysts.
The work covered up to this date includes the completion of the Tasks planned for WP1, which led to the publication of 3 articles. This enabled us to contribute to the progress on the understanding of the mechanistic features of Fe-mediated cross-couplings, which have been remianing obscure for the last decades.
The Tasks discussed in WP2 are also almost completed, and significant results have been gathered in this WP to efficiently tackle the WP3 of the project. Indeed, success of WP3 strongly relied on the development of tandem C-H activation / C-C cross-coupling sequences involving iron-based catalysts, that were developed during the past two years in the frame of this project.
The Tasks discussed in WP2 are also almost completed, and significant results have been gathered in this WP to efficiently tackle the WP3 of the project. Indeed, success of WP3 strongly relied on the development of tandem C-H activation / C-C cross-coupling sequences involving iron-based catalysts, that were developed during the past two years in the frame of this project.
The understanding of the mechanistic facets of iron-based cross-couplings significantly goes beyond the state of the art owing to the results gathered in WP1, since novel, unprecedented coupling mechanisms relying on two-electron processes were unveiled for the first time. The preliminary results gathered in WP2 also lead to unprecedented reactivities governed by synergistic effects between iron catalysts and main group salts, which will be reported in due time. Moreover, we also reported in the frame of the project a new kind of iron-based non-innocent complex which displays an unprecedented stability, thus also going beyond the state of the art in terms of coordination chemistry of non-innocent platforms.
We anticipate that, at the end of the project, the success of WP3 will also significantly go beyond the state of the art in terms of catalytic C-H activation strategies relying on non-noble metals.
We anticipate that, at the end of the project, the success of WP3 will also significantly go beyond the state of the art in terms of catalytic C-H activation strategies relying on non-noble metals.