Theoretical Study of the Catalytic Hydrogenation of Alkenes by a Disilaferracyclic Complex: Can the Fe-Si σ-Bond-Assisted Activation of H-H Bonds Allow Development of a Catalysis of Iron?

The mechanisms associated with the hydrogenation of alkenes catalyzed by the iron complex Fe(cis-CO)2 {o-(SiMe2 )2 C6 H4 }2 (H)2 (1) were investigated by DFT calculations. The complex 1 has a structure in which the iron center is bonded to four silicon atoms and two hydrides. Secondary Si···H···Si interactions were also observed. The exchange of a 1,2-bis(dimethylsilyl)benzene ligand with ethylene and hydrogen gives a disilaferracycle bearing η2 -(CH2 ═CH2 ) and η2 -H2 ligands. The catalytic cycle initiated from the disilaferracycle involves cleavage of a H-H linkage assisted by an Fe-Si bond to form Fe-H and η1 -(H-Si) moieties (step 1), hydrogen migration from the Fe-H group to the η2 -(CH2 ═CH2 ) ligand which accomplishes the insertion of ethylene into the Fe-H bond (step 2), and reaction of the resulting β-agostic ethyl moiety with the η2 -(H-Si) group to form ethane on the iron atom (step 3). The octahedral geometry of 1 as well as the presence of π-acidic CO ligands and Fe-Si σ-bonds contributes to all of the catalytic intermediates and the transition states being in the low-spin state. Steps 1 and 3 correspond to the σ-complex-assisted metathesis (σ-CAM) mechanisms proposed by Perutz and Sabo-Etienne, suggesting that these mechanisms can assist in the design of iron-based hydrogenation catalysts operating under mild conditions.