Prospects of ethylene hydroformylation beyond Rh-based catalysts

Abstract

Rh-based homogeneous catalysts with phosphine ligands have been typically used for catalysing hydroformylation reactions. Heterogenisation of Rh-based systems, however, introduces a side-reaction of ethylene hydrogenation. In order to enhance reaction selectivity, (1) immobilization of single atom catalysts onto supports like polymers, ZnO or CeO and (2) the use of promoters such as Co, Mo, V, and alkali metals have emerged as new strategies. However, all these studies involve the use of Rh, an expensive noble metal, as a catalyst. With the intention of designing a non-Rh-based catalyst with single site reactivity for ethylene hydroformylation, we have, for the first time, computationally investigated the role of UiO-68 decorated NHC-Cu(I)-H catalyst in catalysing the reaction. Mechanistic investigations suggest that it can selectively transform ethylene to propanal and can act as an alternative to the homogeneous Wilkinson's catalyst and also to various Rh-based heterogeneous catalysts.