PhD position in synthetic organometallic chemistry and catalysis

Updated: 13 days ago
Location: Rennes, BRETAGNE
Job Type: FullTime
Deadline: 15 Jun 2024

16 Apr 2024
Job Information
Organisation/Company

Université de Rennes
Department

Chemistry
Research Field

Chemistry » Inorganic chemistry
Chemistry » Homogeneous catalysis
Researcher Profile

First Stage Researcher (R1)
Country

France
Application Deadline

15 Jun 2024 - 12:00 (Europe/Paris)
Type of Contract

Temporary
Job Status

Full-time
Hours Per Week

40
Offer Starting Date

1 Oct 2024
Is the job funded through the EU Research Framework Programme?

Not funded by an EU programme
Is the Job related to staff position within a Research Infrastructure?

No

Offer Description

The large alkaline earths (= Ae) calcium, strontium and barium are attracting interest as inexpensive and abundant s-block alternatives to expensive transition metals for the design of molecular catalysts. Because the reactivity of highly ionic Ae‒O and Ae‒N bonds is now well understood, molecular alkaline-earth complexes can be used to great effect in organic catalysis and for the functionalisation of small molecules, e.g. N2 , CO2, benzene, etc. They display excellent behaviour, combining high reaction rates and original selectivity. Beyond Ae‒O and Ae‒N bonds, our understanding of the organometallic chemistry of Ca, Sr and Ba, which for long remained ignored due the uncontrollable reactivity of Ae‒C bonds, has now improved substantially. However, little is known about Ae‒MP bonds in heterobimetallic complexes combining a large alkaline earth and a p-block metal  (= MP ). This includes derivatives involving a triel (MP = aluminium, gallium, indium) or a pnictogen (MP = antimony and bismuth) metal. Overall, the available studies are limited to structural investigations with light elements; the intricacies of the Ae–MP bond have seldom been investigated. This constitutes a major impediment to the implantation of these compounds in applied chemistry.

In this context, the three objectives of the PhD project are:

1) Synthesising new families of heterobimetallic complexes that contain direct Ae-to-metal bonds between alkaline earths (Ae = Ca, Sr, Ba) and a triel (Mp = Al, Ga, In) or a pnictogen (MP = Sb, Bi).

2) Investigating bonding and structural patterns, notably to understand the nature of Ae–MP bonds.

3) Assessing their ability to catalyse in controlled and atom-efficient fashion the dehydrocoupling of hydrogallanes, hydrostibanes, and hydrobismuthanes (respectively R2 GaH, R2 SbH and R2 BiH) with amines, in order to construct N–MP bonds in high value-added products.   

The project involves a large amount of synthetic organometallic chemistry with air-sensitive compounds, that will require to work under inert atmosphere. Once prepared and characterised by conventional methods (NMR spectroscopy in solution, X-ray diffraction crystallography, FTIR, etc.), the new metal complexes will be utilised in homogenous catalysis. Understanding the intimate nature of the new Ae–Pn bonds and of the factors governing the structure, stability and chemical properties of these complexes, will be a key aspect, and DFT investigations of the compounds will be performed in the course of the project.

The PhD will be carried out with a co-tutella agreement between the Université de Rennes (Rennes, France) and the University Babes-Bolyai (Cluj-Napoca, Romania), who co-fund the PhD grant. The recruited PhD student will spend equal shares of time in the two institutions to carry out the research project. 


Requirements
Research Field
Chemistry » Inorganic chemistry
Education Level
Master Degree or equivalent

Skills/Qualifications

Applicants must hold a Master Degree in molecular chemistry. 

We are looking to recruit a dynamic, highly motivated student with a strong affinity for synthetic organometallic chemistry. Previous experience in this field is a requirement. A flair for molecular catalysis is recommended, and an interest in quantum mechanics (DFT) will also be an advantage. The ability to carry out literature searches autonomously and to keep up to date with the pertinent literature is compulsory. 

The recruited student must be able to work in relative autonomy, and must show the capacity to embrace the project by gradually insufflating his/her own ideas in the investigations. (S)He must be mobile and opened to the idea of working in two different, multi-cultural laboratories in France and Romania.

A very good command of English language is mandatory.


Specific Requirements

Mobility is required. The PhD position is co-financed by the Collège Doctoral de Bretagne, France, and by the University Baes-Bolyai, in Cluj-Napoca, Romania. The full research grant is already secured. The PhD student will carry out his/her diploma within a co-tutella framework between the University of Rennes, in France, and the Babeş-Bolyai University. The PhD will be conducted under the supervision of Dr Yann SARAZIN (CNRS Research director, Rennes) and Prof Cristian SILVESTRU (Cluj-Napoca). It is expected that the PhD student will spend equal amounts of time in Rennes and in Cluj-Napoca to carry out the 36-month research project. (S)He will enjoy the unique possibility to travel and work in two different laboratories, hence acquiring an array of soft skills and experience, in addition to the usual scientific skills expected from a PhD training in chemical sciences. (S)He will graduate and receive a PhD diploma from both universities.

An additional envelop of 4,800 € is provisioned on top of the regular PhD grant by the University of Rennes to cover mobility costs within the co-tutella framework.


Languages
ENGLISH
Level
Excellent

Research Field
Chemistry » Inorganic chemistry

Additional Information
Benefits

The PhD grant is provisioned by the Collège Doctoral de Bretagne and the University Babes-Bolyai and covers the full salary of the PhD student for 36 months, amounting to ca. 1760 € (net) pcm. 

An additional envelop of 4,800 € is also provided by the Collège Doctoral de Bretagne on top of the regular PhD grant to cover travel costs between Rennes (France) and Cluj-Napoca (Romania) in the context of the PhD co-tutella agreement.

The student will be registered to both the Univerté de Rennes and the Univertiy Babes-Bolyai, and will be awarded a PhD degree from both universities. (S)He will enjoy usual benefits, including insurance and health care, for university students in France and Romania. 


Eligibility criteria

The PhD will start on October 1, 2024.

Applicants must hold a Master Degree in molecular chemistry.

A very good command of English, and the mobility required to work in two different laboratories in France and Romania, are mandatory. 


Selection process

Applicants must  send by email their up-to-date curriculum vitae, academic records and motivation letter to Dr Yann Sarazin ([email protected] ) and Prof Cristian Silvestru ([email protected] ). Please also provide the contact details of two referees who will be requested to supply a recommandation letter. 

An interview will be set up through visio conference with the applicants who will have been selected on a  shortlist. A final decision will be communicated no later than June, 30th, 2024.


Additional comments

For further information about this position, please contact Dr Yann Sarazin ([email protected] ) and Prof Cristian Silvestru ([email protected] ).

 

 

References related to the project

Barium phosphidoboranes and related calcium complexes. G. Duneş, P. M. Chapple, S. Kahlal, T. Roisnel, J.-F. Carpentier, J.-Y. Saillard, Yann Sarazin. Dalton Trans.2024, in press, DOI: 10.1039/d4dt00487f

Bis(imino)carbazolate lead(II) fluoride and related halides. P. M. Chapple, G. Hamdoun, T. Roisnel, J.-F. Carpentier, H. Oulyadi, Y. Sarazin. Dalton Trans. 2021, 50, 9021-9025. DOI: 10.1039/D1DT01615F

Metal-metal bonded alkaline-earth distannyls. P. M. Chapple, J. Cartron, G. Hamdoun, S. Kahlal, M. Cordier, H. Oulyadi, J.-F. Carpentier, J.-Y. Saillard, Y. Sarazin. Chem. Sci.2021, 12, 7098-7114, DOI: 10.1039/D1SC00436K

Bis(imino)carbazolate: a master key for barium chemistry. P. M. Chapple, S. Kahlal, J. Cartron, T. Roisnel, V. Dorcet, M. Cordier, J.-Y. Saillard, J.-F. Carpentier, Y. Sarazin. Angew. Chem. Int. Ed.2020, 59, 9120-9126. DOI: 10.1002/anie.202001439    Hot paper Highlighted in Chemistry Views (link )

Mixed triorganobismuthines RAr2 Bi [Ar = C6 F5 , 2,4,6-(C6 F5 )3 C6 H2 ] and hypervalent racemic Bi-chiral diorganobismuth(III) bromides RArBiBr (Ar = C6 F5 , Mes, Ph) with the ligand R =2-(Me2 NCH2 )C6 H4 . Influences of the organic substituent. M. Olaru, M. Nema, A. Soran, H. J. Breunig, C. Silvestru, Dalton Trans.2016, 45, 9419-9428; DOI: 10.1039/C5DT05074J    

A general route to monoorganopnicogen(III) (M = Sb, Bi) compounds with a pincer (N,C,N) group and oxo ligands G. Strîmb, A. Pöllnitz, C. I. Raţ, C. Silvestru, Dalton Trans.2015,44, 9927-9942, DOI: 10.1039/c5dt00603a

 


Work Location(s)
Number of offers available
1
Company/Institute
Institut des Sciences Chimiques de Rennes, UMR CNRS 6226
Country
France
State/Province
Bretagne
City
Rennes
Postal Code
35042
Street
263 avenue du Général Leclerc
Geofield


Number of offers available
1
Company/Institute
Universitatea Babes-Bolyai, Faculty of Chemistry and Chemical Engineering
Country
Romania
City
Cluj-Napoca
Postal Code
RO-400028
Street
Arany Janos Str. no. 11
Geofield


Where to apply
E-mail

[email protected]

Contact
State/Province

Bretagne
City

RENNES
Website

https://www.univ-rennes.fr
https://iscr.univ-rennes.fr/
https://chem.ubbcluj.ro/en/index.html
Street

263 avenue du Général Leclerc
Postal Code

35042

STATUS: EXPIRED