Selective Synthesis of Site-Differentiated Fe₄S₄ and Fe₆S₆ Clusters

Obtaining rational control over the structure and nuclearity of metalloclusters is an ongoing challenge in synthetic Fe-S cluster chemistry. We report a new family of tridentate imidazolin-2-imine ligands L(NIm^R)₃ that can bind [Fe₄S₄]²⁺ or [Fe₆S₆]³⁺ clusters, depending on the steric profile of the ligand and the reaction stoichiometry. A high-yielding synthetic route to L(NIm^R)₃ ligands (where R is the imidazolyl N substituents) from trianiline and 2-chloroimidazolium precursors is described. For L(NIm^Me)₃ (tris(1,3,5-(3-( N, N-dimethyl-4,5-diphenylimidazolin-2-imino)phenylmethyl))benzene), metalation with 1 equiv of [Ph₄P]₂[Fe₄S₄Cl₄] and 3 equiv of NaBPh₄ furnishes a mixture of products, but adjusting the stoichiometry to 1.5 equiv of [Ph₄P]₂[Fe₄S₄Cl₄] provides (L(NIm^Me)₃)Fe₆S₆Cl₆ in high yield. Formation of an [Fe₆S₆]³⁺ cluster using L(NIm^Tol)₃ (tris(1,3,5-(3-( N, N-bis(4-methylphenyl)-4,5-diphenylimidazolin-2-imino)phenylmethyl))benzene) is not observed; instead, the [Fe₄S₄]²⁺ cluster [(L(NIm^Tol)₃)(Fe₄S₄Cl)][BPh₄] is cleanly generated when 1 equiv of [Ph₄P]₂[Fe₄S₄Cl₄] is employed. The selectivity for cluster nuclearity is rationalized by the orientation of the imidazolyl rings whereby long N-imidazolyl substituents preclude formation of [Fe₆S₆]³⁺ clusters but not [Fe₄S₄]²⁺ clusters. Thus, the structure and nuclearity of L(NIm^R)₃-bound Fe-S clusters may be selectively controlled through rational modification the ligand's substituents.