Utilizing a hexadentate ligand platform, a high-spin trinuclear iron complex of the type (tbsL)Fe3(thf) was synthesized and characterized ([tbsL]6- = [1,3,5-C6H 9(NPh-o-NSitBuMe2)3]6-). The silyl-amide groups only permit ligation of one solvent molecule to the tri-iron core, resulting in an asymmetric core wherein each iron ion exhibits a distinct local coordination environment. The triiron complex ( tbsL)Fe3(thf) rapidly consumes inorganic azide ([N 3]NBu4) to afford an anionic, trinuclear nitride complex [(tbsL)Fe3(μ3-N)]NBu4. The nearly C3-symmetric complex exhibits a highly pyramidalized nitride ligand that resides 1.205(3) Å above the mean triiron plane with short Fe-N (1.871(3) Å) distances and Fe-Fe separation (2.480(1) Å). The nucleophilic nitride can be readily alkylated via reaction with methyl iodide to afford the neutral, trinuclear methylimide complex (tbsL)Fe 3(μ3-NCH3). Alkylation of the nitride maintains the approximate C3-symmetry in the imide complex, where the imide ligand resides 1.265(9) Å above the mean triiron plane featuring lengthened Fe-Nimide bond distances (1.892(3) Å) with nearly equal Fe-Fe separation (2.483(1) Å).
ASJC Scopus subject areas
- Colloid and Surface Chemistry