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Base-Free Iron Hydrosilylene Complexes via an α-Hydride Migration that Induces Spin Pairing

Author:
Smith, Patrick W., Tilley, T. Don
Source:
Journal of the American Chemical Society 2018 v.140 no.11 pp. 3880-3883
ISSN:
1520-5126
Subject:
carbon-hydrogen bond activation, chemical bonding, hydrogen, hydrogenation, iron, ruthenium
Abstract:
Two new base-free hydrosilylene complexes of iron were synthesized using the novel starting material Cp*(ⁱPr₂MeP)FeMes. These Cp*(ⁱPr₂MeP)Fe(H)SiHR (R = DMP, Trip) complexes are in equilibrium with the corresponding iron silyl complexes, Cp*(ⁱPr₂MeP)FeSiH₂R, which can be trapped and characterized for R = Trip. Unlike the Ru analogues, the Fe silylene complex with R = DMP is observed to undergo an intramolecular C—H activation involving formal addition of a benzylic C—H bond across the Fe—Si bond. This increased activity for bond activations is also observed for reactions with hydrogen, where Fe reacts faster than a Ru analog to form the hydrogenation product, Cp*(ⁱPr₂MeP)H₂FeSiH₂DMP.
Agid:
6033139