A sustainable future lies in the use of first row, low cost, low toxicity, Earth-abundant
metals. Despite this, the metals that are most abundant have yet to be widely adopted by the
global community. The overarching aim at the outset of the project was to ask the question:
Why is this?
Why do expensive metals such as; platinum, palladium and rhodium dominate?
Why does the synthetic chemist not instinctively use iron, manganese or cobalt?
The simple answer: The non-expert chemist is simply not equipped to try. Many modern synthetic methods for the reductive functionalisation of alkenes and alkynes
rely on the use of air- and moisture-sensitive pre-catalysts or reagents, which are challenging
to handle, store and transport. In the ideal scenario, all reagents and pre-catalysts would be
air- and moisture-stable solids that are easily handled, and applicable in large-scale processes
with minimal associated hazards.
This project entailed the development of a simple pre-catalyst activation protocol using a
safe and easily handled reagent (NaOtBu) with wide commercial availability. This has
allowed generic access to sustainable first-row transition metal (Fe, Co, Mn, Ni) low
oxidation-state catalysis across a wide range of reductive alkene and alkyne functionlisation
reactions (hydroboration, hydrosilylation, hydrogenation, hydrovinylation and [2π+2π]
cyclisation reactions). Using this straightforward catalyst activation strategy a new regiodivergent cobalt-catalyst alkene hydrosilylation manifold was discovered and
mechanistically explored. Taken together, all results are suggestive of a new and unique catalyst activation mechanism
that is primed for future reaction, catalyst and mechanistic development
