Origin of the Ligand Ring-Size Effect on the Catalytic Activity of Cationic Calcium Hydride Dimers in the Hydrogenation of Unactivated 1-Alkenes.

Recently, it was shown that the double Ca-H-Ca-bridged calcium hydride cation dimer [LCaH 2 CaL] 2+ when stabilized by a larger macrocyclic N,N',N'',N''',N''''-pentadentate ligand showed evidently higher activity than when stabilized by a smaller N,N',N'',N'''-tetradentate ligand in the catalytic hydrogenation of unactivated 1-alkenes. In this DFT-mechanistic work, the origin of the observed ring-size effect is examined in detail using 1-hexene, CH 2 =CH 2 and H 2 as substrates. It is shown that, at room temperature, both the N,N',N'',N''',N''''-stabilized dimer and the monomer are not coordinated by THF in solution, while the corresponding N,N',N'',N'''-stabilized structures are coordinated by one THF molecule mimicking the fifth N-coordination. Catalytic 1-alkene hydrogenation may occur via anti-Markovnikov addition over the terminal Ca-H bonds of transient monomers, followed by faster Ca-C bond hydrogenolysis. The higher catalytic activity of the larger N,N',N'',N''',N''''-stabilized dimer is due to not only easier formation of but also due to the higher reactivity of the catalytic monomeric species. In contrast, despite unfavorable THF-coordination in solution, the smaller N,N',N'',N'''-stabilized dimer shows a 3.2 kcal mol -1 lower barrier via a dinuclear cooperative Ca-H-Ca bridge for H 2 isotope exchange than the large N,N',N'',N''',N''''-stabilized dimer, mainly due to less steric hindrance. The observed ring-size effect can be understood mainly by a subtle interplay of solvent, steric and cooperative effects that can be resolved in detail by state-of-the-art quantum chemistry calculations.