Hexene hydrogenation catalysed by the complex monohydrid complexes: A DFT study of associated vs dissociated pathways

A DFT study was conducted to elucidate the mechanism of hexene hydrogenation catalysed by a series of ruthenium (II) monohydride catalysts: RuH(CO)(Cl)(LL') where L and L' represent C(cyclohexyl), Me (methyl) and IMe (N, N '-bis (mesityl) imidazole-2-ylidene). This investigation explores the feasibility of two different proposed mechanisms: the first describes the dissociated pathway and exploits a single phosphine complex. The second is the associative one and uses a two phosphines complex. The detailed pathways have been explored for the catalyst model with L = L' = Me. Three possibilities have been supported for the dissociative route. Pathway (A) begins with a phosphine release. The initial addition of hexane or a dihydrogen molecule on the ruthenium catalyst generates the pathways (B) and (C), respectively. Pathways (B) and (C) merge with the pathway (A) before and after the first proton transfer, respectively. Activation energies in the first hydrogen migration (the key-step of the mechanism) are close. Therefore, both mechanisms (A) and (B) are possible but the former is more probable. The substitution of the catalyst model RuHCl(CO)(PMe3)(2) by the real catalysts RuHCl(CO)(PCy3)(2) or RuHCl(CO)(IMes)(PMe3) shows no significant influence on the energetic barriers of hexene hydrogenation mechanism. The energy profile of the first hydrogen migration for the catalyst RuHCl(CO)(PCy3)(2) is characteristic of a concerted asynchronous mechanism while our calculation led to two separated synchronous steps when the model catalyst is used. The associative pathway (D) integrates the two experimentally detected intermediates and generates activation energies close to those of dissociative pathways (A) and (B). The rationale to explain the experimentally detected species is achieved by considering the four proposed mechanisms where they occur simultaneously and with different rates (ie. The dissociative mechanism has the highest rate). (C) 2020 Elsevier Inc. All rights reserved.