Bifunctional transition metal pincer complexes for activation of small molecules

ORAU Grant

The project is aimed at the preparation of novel transition metal pincer complexes and their application in activation of small molecules and homogeneous catalysis for transformation of organic and inorganic substrates into value added products. Over the past few decades, pincer complexes have attracted significant interest from a large number of research groups.1 Such
compounds have been studied in C-H, C-C, C-N, C-O and recently N-H and O-H activation reactions.1 Whereas chemistry of pincer complexes of symmetrical EXE ligands with neutral 2e donor side-arms E (e.g. NR2, PR2) and either neutral or anionic 2e donors in the bridgehead position X (e.g. C¯, N¯, N) is now at the advanced stage of development,1 the chemistry of unsymmetrical pincer complexes with different side-arm donors, such as PXN, PXS, etc., is studied to a lesser extent.1,2 Such unsymmetrical substitution in the side-arm positions of pincer ligands allows for fine-tuning of stability vs reactivity of pincer complexes, often affecting the selectivity of catalytic transformations. Therefore, we mainly focused at the design and catalytic applications of unsymmetrical imino-, amino-and amidophosphine pincer complexes with abundant and cheap base transition metals, such as Ni, Co, Fe, Zn. For the reactivity comparison
purposes, preparation and reactivity studies of similar bidentate ligands and their transition metal complexes with first-row transition metals were also targeted.