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

[Image: see text] 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 (Cl(3)Si)CpFe(CO)(2) (Cl(3)SiFp) by substitution of chloride with pyrrolide or 3-methylindolide, respectively. Analogously, nucleophilic substitution of Cl with pyrrolide on the anionic Fe(0) synthon Cl(3)SiFe(CO)(4)(–) generates the (tripyrrolyl)silyl ligand, bound to the iron tetracarbonyl fragment. The bulkier 2-mesitylpyrrolide substitutes a maximum of 2 chlorides on Cl(3)SiFp under the same conditions. The tridentate, trianionic nucleophile tmim (tmimH(3) = 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(C(4)H(8)O)(3)SiFe(CO)(4)(–). The bidentate, monoanionic nucleophile 2-(dipp-iminomethyl)pyrrolide ((Dipp)IMP, dipp = 2,6-diisopropylphenyl) shows chloride displacement and addition of a second (Dipp)IMP 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.