Use of a Compact Tripodal Tris(bipyridine) Ligand to Stabilize a Single-Metal-Centered Chirality: Stereoselective Coordination of Iron(II) and Ruthenium(II) on a Semirigid Hexapeptide Macrocycle
作者:Yuka Kobayashi、Masaru Hoshino、Tomoshi Kameda、Kazuya Kobayashi、Kenichi Akaji、Shinsuke Inuki、Hiroaki Ohno、Shinya Oishi
DOI:10.1021/acs.inorgchem.8b00416
日期:2018.5.7
the Fe(II)–peptide complex has an apparent C3-symmetric conformations on the NMR time scale, while the peptide backbone is subject to dynamic conformational exchange between three asymmetric β/γ conformations and one C3-symmetric γ/γ/γ conformation. The semirigid cyclic hexapeptide preferentially arranged these conformations of the small octahedral Fe(II)–bipyridine complex, as well as the Ru(II) congener
设计并合成了含有三个2,2'-联吡啶部分作为侧链的Fe(II)配位六肽。具有三个[(2,2'-联吡啶)-5-基]甲环六肽- d -丙氨酸(d -Bpa5)残基,其中ð -Bpa5和甘氨酸交替排列用3重旋转对称,具有铁协调(II)形成具有金属中心手性的单个面部-Λ构型的1:1八面体Fe(II)-肽复合物。NMR光谱和分子动力学模拟表明,Fe(II)-肽配合物具有明显的C 3在NMR时标上具有对称的构象,而肽主链则在三个非对称的β/γ构象和一个C 3对称的γ/γ/γ构象之间进行动态构象交换。半刚性环状六肽优先排列小八面体Fe(II)-联吡啶配合物以及Ru(II)同源物的这些构象,以支撑以金属为中心的手性的单一构型。