PhD in organometallic chemistry M/F

Updated: 6 months ago
Location: Tremblay en France, LE DE FRANCE
Deadline: 08 Jul 2019

The PhD will be conducted in the SMAc óSmall Molecule Activationó team of the Laboratory for Coordination Chemistry, under the guidance of Dr. Antoine Simonneau. The funding is already ensured by an ERC Starting grant (OrFuNCo, contract n∞ 757501).

Direct conversion of dinitrogen into more reactive sources of the element N has been an intensively studied topic for more than a century.
Beyond the fundamental challenge of activating this very inert molecule,
the social concern of guaranteeing enough N-containing fertilizers for human agriculture has been deeply linked to the past and current research effort on nitrogen fixation.
The industrial Haber-Bosch (HB) process nowadays allows the production of millions of tons of ammonia (NH3) which is subsequently converted into fertilizers (ca. æ of the production) and bulk or fine chemicals.
This, however, occurs at a high fossil resources and energy (1ñ2% of the World's annual energy consumption) expense.
Moreover, this process is indirectly responsible for the production of a large amount of greenhouse gas waste (CO2), while abusive use of nitrogen fertilizers has negatively impacted our environment.
Reconsidering the use of N2, a very abundant molecule, is a challenge modern chemistry has to take up. In this perspective, the use of molecular dinitrogen complexes appears promising.
These fascinating entities have allowed catalytic N2 reduction to ammonia under ordinary temperature and pressure, as well as the formation of NñC bond between dinitrogen and organic substrates, eventually affording organonitrogen compounds.
We have recently tackled N2 chemistry with the aim of developing unprecedented methodologies based on metal-main group and metal-metal cooperativity.

We are aiming at finding new cooperative mechanisms that could lead to the transformation of N2 into value-added nitrogen compounds in the coordination sphere of a metal.
The candidate will be proposed several intercrossed axis of research:

1. N2/CO2 coupling for carbamate synthesis inspired by the Frustrated Lewis Pair (FLP) chemistry,

2. Study of Earth-abundant dinitrogen complexes' reactivity in the reaction we have developed,

3. Bimetallic N2 splitting for the production of organonitrogen compounds,

4. Reactivity of N2 ligand with organometallacycles to study insertions and cycloadditions elementary steps.

Low-valent N2 complexes syntheses and studies of the reactivity thereof will be overall central to this Ph. D. project.

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