Clendening Reese A, Zeller Matthias, Ren Tong
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.
Inorg Chem. 2022 Aug 29;61(34):13442-13452. doi: 10.1021/acs.inorgchem.2c01743. Epub 2022 Aug 2.
Reported herein are new Fe bis-alkynyl complexes [Fe(L)(CR)]BPh based on tetra macrocycle (L = HMTI = -5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene; ; R = CH (), CH (), SiMe ()) and tetra macrocycle (L = HMC = -5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane; ). These complexes have been characterized using single-crystal X-ray diffraction, electronic absorption spectroscopy, and cyclic and differential pulse voltammetry. Spectroelectrochemical studies of and allowed for investigation of the Fe oxidation state, which revealed a strong dependence on the nature of the macrocycle for both the energies of the Fe to CPh 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 than in . These findings are rationalized on the basis of the relative energies of the formally metal-centered orbitals density functional theory calculations.
本文报道了基于四氮杂大环（L = HMTI = -5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四碳-1,3,8,10-四烯； ；R = CH ()、CH ()、SiMe ()）和四氮杂大环（L = HMC = -5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷； ）的新型铁双炔基配合物[Fe(L)(CR)]BPh 。这些配合物已通过单晶X射线衍射、电子吸收光谱以及循环伏安法和差分脉冲伏安法进行了表征。对 和 的光谱电化学研究使得能够对铁的氧化态进行研究，结果表明，对于铁到CPh的金属-配体电荷转移（MLCT）能量和ν(C≡C)而言，其对大环的性质有很强的依赖性。尽管 在对形式上的金属氧化态的敏感性方面比 高得多，但ν(C≡C)还受到氧化态的进一步影响。基于形式上以金属为中心的轨道的相对能量 密度泛函理论计算，对这些发现进行了合理化解释。
