RESEARCH
Acknowledgments
Skill Development
Group members in the Jayaraman lab will actively gain experience with a variety of synthetic, analytical, and computational methods. Key skills include: (i) using Schlenk lines and gloveboxes for synthesizing air- and moisture-sensitive main-group compounds; (ii) applying analytical tools like X-ray crystallography, NMR, EPR, UV-vis and IR spectroscopy, mass spectrometry, and electrochemistry for structural characterization; and (iii) employing computational approaches such as density functional theory to examine molecular structures, bonding situation and reaction mechanisms.
Ambiphilic Behavior in Main-Group Compounds
Electrophiles, Nucleophiles, and Ambiphiles
A reactive atomic center in a molecule, compound, or complex acts as an electrophile when it has a vacant orbital, and as a nucleophile when it has a filled orbital. If both a vacant and a filled orbital are present at the same atomic center, it displays ambiphilic behavior. This electronic situation—and the resulting ambiphilic properties—are commonly found in transition-metal complexes, making them essential in numerous chemical fields ranging from catalysis to material science.
Main-Group Compounds and Their Limitations
While transition-metal complexes have a wide range of applications, main-group compounds with similar properties are still emerging. Especially in catalysis, the main limitation is that main-group compounds often cannot perform many fundamental reactions as effectively as transition-metal complexes. For example, compounds centered on group 13 to group 15 elements can activate the bonds (oxidative addition) of small molecules, but struggle to transfer these activated molecules to unsaturated substrates for the production of fine chemicals or their building blocks. Meanwhile, group 16-centered compounds can transfer activated molecules (reductive elimination) to organic substrates but are less effective at activating the small molecules themselves.
Balancing Reactivity in Main-Group Compounds
For main-group compounds to serve as alternatives or complements to transition-metal complexes, the kinetics and thermodynamics of their elementary reactions must be well balanced. Achieving this balance is critical for advancing their applications.
Research Directions
Our research group aims to design and optimize a variety of ambiphilic main-group compounds using sustainable elements such as carbon, silicon, boron, aluminum, phosphorus, and bismuth. We seek to employ these compounds as stoichiometric reagents and catalysts for energy-relevant chemical synthesis. Additionally, we will explore their use, or the use of their derivatives, as: (i) ligands for s, p, and f block elements; (ii) ligands for transition-metal-based heterogeneous materials; (iii) dopants for π-conjugated materials; and (iv) potential agents with biological activity.