UC Santa Barbara

Reaction of FeBr₂ with Li(N═C^tBu₂) (0.5 equiv) and Zn⁰ (2 equiv) results in the formation of the formally mixed-valent cluster [Fe₄Br₂(N═C^tBu₂)₄] (1) in moderate yield. The subsequent reaction of 1 with Na(N═C^tBu₂) results in formation of [Fe₄Br(N═C^tBu₂)₅] (2), also in moderate yield. Both 1 and 2 were characterized by zero-field ⁵⁷Fe Mössbauer spectroscopy, X-ray crystallography, and superconducting quantum interference device magnetometry. Their tetrahedral [Fe₄]⁶⁺ cores feature short Fe-Fe interactions (ca. 2.50 Å). Additionally, both 1 and 2 display S = 7 ground states at room temperature and slow magnetic relaxation with zero-field relaxation barriers of U_eff = 14.7(4) and 15.6(7) cm^-1, respectively. Moreover, AC magnetic susceptibility measurements were well modeled by assuming an Orbach relaxation process.