Synthesis of N-Heterocycle Substituted Silyl Ligands within the Coordination Sphere of Iron

N-Heterocycle-substituted silyl iron complexes have been synthesized by nucleophilic substitution at trichlorosilyl ligands bound to iron. The homoleptic (tripyrrolyl)- and tris(3-methylindolyl)silyl groups were accessed from (Cl₃Si)CpFe(CO)₂ (Cl₃SiFp) by substitution of chloride with pyrrolide or 3-methylindolide, respectively. Analogously, nucleophilic substitution of Cl with pyrrolide on the anionic Fe(0) synthon Cl₃SiFe(CO)₄ ^- generates the (tripyrrolyl)silyl ligand, bound to the iron tetracarbonyl fragment. The bulkier 2-mesitylpyrrolide substitutes a maximum of 2 chlorides on Cl₃SiFp under the same conditions. The tridentate, trianionic nucleophile tmim (tmimH₃ = tris(3-methylindol-2-yl)methane) proves reluctant to perform the substitution in a straightforward manner; instead, ring-opening and incorporation of THF occurs to form the tris-THF adduct tmim(C₄H₈O)₃SiFe(CO)₄ ^-. The bidentate, monoanionic nucleophile 2-(dipp-iminomethyl)pyrrolide (^DippIMP, dipp = 2,6-diisopropylphenyl) shows chloride displacement and addition of a second ^DippIMP moiety on the imine backbone. The heterocycle-based silyl ligands were shown to be sterically and electronically tunable, moderately electron-donating ligands. The presented approach to new silyl ligands avoids strongly reducing conditions and potentially reactive hydrosilane intermediates.