The project aims to selectively convert bioethanol to butanol, a better fuel additive, using a tandem dehydrogenation/Aldol condensation/rehydrogenation process. Using Cp*Ir(PhPyOH) (1) along with [Tp’Ni(OH)2] (2) or [IprCuOH] (3) has achieved over 99% selectivity with around 40% conversion. The researcher is working to understand the mechanistic details of the Aldol condensation step to explain the high selectivity and inhibition factors by carrying out NMR assisted stoichiometric reactions and isolating intermediates. Modifying [Tp’Ni(OH)2] and [IprCuOH] and studying cobalt and iron

1. New Route to C4 Alcohols (University of Rochester, March 2016 – Present):
The project goal is to convert bio-ethanol selectively to butanol, a better fuel additive, using
a tandem dehydrogenation/Aldol condensation/rehydrogenation route, the Guerbet
process. Use of Cp*Ir(PhPyOH) (1) along with [Tp’Ni(OH)2 ] (2) or [IprCuOH] (3) has lead us to
achieve >99% selectivity with about 40%
conversion (J. Am. Chem. Soc. 2015, 137,
14264). The second step of the reaction,
Aldol condensation, is found to be the
decisive step towards selectivity and the
outstanding selectivity achieved by using
[Tp’Ni(OH)2] & [IprCuOH] is certainly
connected to their steric and electronic
features. Presently I’m working on the
mechanistic details of the Aldol condensation step in order to understand the root of high-
selectivity and the reaction inhibition factors. My priorities include carrying NMR assisted
stoichiometric reactions and isolation of the reaction intermediates. Modifying [Tp’Ni(OH)2 ]
& [IprCuOH] with different structural and electronic facets and studying their impact on the
catalytic activity (quest for finding a ‘better base’ & condition to achieve complete
conversion) and developing simple cobalt and iron catalysts for the acceptorless
dehydrogenation of alcohols are also under progress.