Synthesis and characterization of new pacman-type transition metal complexes and their application as nitrogenase mimics in the catalytic dinitrogen activation
Final Report Abstract
We have synthesised two new acyclic dipyrrin compounds and two new Schiff-base macrocycles. Whilst these macrocycles are not readily oxidised to their dipyrrin congeners, we hope that this may be possible after coordination to late transition metals. We have prepared two new copper(II) macrocyclic complexes and the investigation on their redox behaviour through electrochemistry and EPR spectroscopy is currently under way in the group of Dr. Love, as well as their reactivity towards N2 and CO2. Unfortunately, the transmetalation reactions with a variety of Mo-precursors, e.g. MoCl3(thf)3 were not successful. The reactivity of FeBr(L1) towards dinitrogen was investigated by the reduction of the complex with both Na-amalgam and potassium graphite under an atmosphere of dinitrogen. Although a reaction definitely occurred, the respective products could not yet be crystallised.
Publications
- Towards dipyrrins: oxidation and metalation of acyclic and macrocyclic Schiff-base dipyrromethanes. Dalton Trans., 2015,44, 2066-2070
D. Betz, J. R. Pankhurst, C. Finn, T. Cadenbach, J. B. Love
(See online at https://doi.org/10.1039/c4dt03592e)
