Research

Chemical Sciences

Title :

Si–H bond activation and its applications in homogeneous catalysis

Area of research :

Chemical Sciences

Focus area :

Homogeneous Catalysis, Silicon Chemistry

Principal Investigator :

Dr. Ramaraj Ayyappan, Indian Institute of Science Education and Research (IISER) Thiruvananthapuram, Kerala

Timeline Start Year :

2024

Timeline End Year :

2027

Contact info :

Details

Executive Summary :

Different ligand platforms based on phosphine and carbene ligands will be developed or utilized for the Si–H bond activation. A series of ligands which could potentially participate in heterolytic cleavage of Si–H bond will be evaluated. Also, neutral, low valent earth abundant Ni(0) metal complexes will be synthesized for the oxidative addition of Si–H bond. The stability of complexes (M–L combination) is governed by Hard-Soft Acid Base (HSAB) interaction. The TM complexes are designed in such way that either it would favour oxidative addition (OA) or cooperative activation pathways. The homolytic activation is favoured by highly electron rich ligands whereas heterolytic activation is facilitated by the presence of internal basic sites in the ligand backbone or the electron deficiency of the metal centre especially cationic centres. The intermediate σ-complex TM-(η²-Si–H) will be isolated and characterized by spectroscopic techniques. Subsequent functionalization with carbonyl, alkenes, CO₂, R–F, RC(O)NH₂ and D₂ will be explored using hydrosilylation reaction. The diverse range of hydrosilylation reaction provides an opportunity to identity a suitable catalyst. Commercially available and stable silanes such as PMHS will be employed for the catalytic applications. The electrophilicity of silicon and the flexible coordination modes of (Si,H) would be focused in this study. Finally, designing novel catalyst and fine tuning the viable pathways to activate Si–H bonds for organic transformations is the scope of this study.

Total Budget (INR):

50,74,872

Organizations involved