ESR3 Project

s-Block Metal-Mediated Hydroelementation

Recruting institution: UAB
Diploma-delivering institutions: UAB, FSU
Thesis co-directors: Agustí Lledós (UAB, Barcelona, ES), Matthias Westerhausen (FSU, Jena, DE)
Secondment host: Italmatch Chemicals (IT)

Objectives

The addition of H-E bonds of amines (hydroamination), phosphanes (hydrophosphanylation), and phosphane oxides (hydrophosphorylation) to multiple bonds (e.g. alkynes) represents an atom-economic reaction that requires a catalyst. s-Block metal complexes are able to promote these addition reactions regioselectively with a significantly increased reactivity for heterobimetallic catalysts (e.g. mixed K/Ca complexes).[1] However, stereocontrol as well as steric and electronic control remain challenging tasks.[2] This project targets mechanistic studies to elucidate not only intermediates but obstacles during the catalytic H-E bond addition across unsaturated substrates to clarify the mode of action for the alkali and alkaline earth metalions.

 

[1] S. M. Härling, B. E. Fener, S. Krieck, H. Görls, M. Westerhausen, Organometallics2018, 37, 4380-4386. S. Ziemann, S. Krieck, H. Görls, M. Westerhausen, Organometallics2018, 37, 924-933. S. M. Härling, S. Krieck, H. Görls, M. Westerhausen, Inorg. Chem. 2017, 56, 9255-9263. F. M. Younis, S. Krieck, T. M. A. Al-Shboul, H. Görls, M. Westerhausen, Inorg. Chem. 2016, 55, 4676-4682.
[2] A. Couce-Rios, A. Lledós, G. Ujaque, Chem. Eur. J.2016, 22, 9311 – 9320.

Expected Results

Addition of H-E bonds across alkynes leads to E/Z-isomeric mixtures. In this project stereocontrol of the s-block metal-mediated addition of H-E-containing substrates onto alkynes with > 95 % of E– or Z-isomeric products will be achieved with catalyst loadings between 2-5 mol-%. Quantum chemical studies will allow to elucidate the influence of the nature of the s-block metal ions (charge, hardness, radius, polarizability) on the energy values of the transition states and hence on the mechanism of the catalytic cycle. We also envision a stereoselective intramolecular hydroelementation of alkenes with ee > 95 %.

Irina Bozhinovska

Irina Bozhinovska

PhD student - ESR 3

My name is Irina Bozhinovska. I come from Kumanovo, Republic of Macedonia. I have obtained a bachelor’s degree in chemistry with honours from Cardiff University. Upon working on my final research project -developing catalyst for water purification I decided for my master’s degree to pursue catalysts as my major. I obtained my master’s degree in catalysis with honours also from Cardiff University. The research of my thesis focused on preforming selective catalytic conversion of glycerol to lactic acid over x-Si-TiOy catalysts under inert atmosphere. During my undergraduate studies I had the opportunity to be selected as a Cardiff Catalysis Institute (CCI) research student under the supervision of Professor Jonathan Bartley.
As a future fellow CCIMC research student I will be investigating the addition of H-E bonds of amines, phosphanes and phopshane oxides to multiple bonds (eg. alkynes). The main aims of my project are mechanistic studies to determine and explain not only the formed intermediates but also the hurdles during the catalytic H-E bond addition across unsaturated substrates. I will perform my ESR3 Project under the supervision of Prof. Agustí Lledós (Universitat Autònoma de Barcelona) and Prof. Matthias Westerhausen (Friedrich Schiller University Jena).