Bis-Alkynyl Complexes of Fe(III) Tetraaza Macrocycles─A Tale of Two Rings

Reported herein are new Fe bis-alkynyl complexes [Fe^III(L)(C₂R)₂]BPh₄ based on tetraimine macrocycle (L = HMTI = meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene; 1a-1c; R = C₆H₅ (a), C₁₀H₉ (b), SiMe₃ (c)) and tetraamine macrocycle (L = HMC = meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane; 2a-2c). These complexes have been characterized using single-crystal X-ray diffraction, electronic absorption spectroscopy, and cyclic and differential pulse voltammetry. Spectroelectrochemical studies of 1a and 2a allowed for investigation of the Fe^II oxidation state, which revealed a strong dependence on the nature of the macrocycle for both the energies of the Fe^II to C₂Ph metal-to-ligand charge transfer (MLCT) and the ν(C≡C). The ν(C≡C) was further influenced by the oxidation state, though sensitivity to the formal metal oxidation state was much higher in the case of 2a than in 1a. These findings are rationalized on the basis of the relative energies of the formally metal-centered orbitals via density functional theory calculations.