57 Fe nuclear resonance vibrational spectroscopic studies of tetranuclear iron clusters bearing terminal iron(III)–oxido/hydroxido moieties,Chemical Science

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57 Fe nuclear resonance vibrational spectroscopic studies of tetranuclear iron clusters bearing terminal iron(III)–oxido/hydroxido moieties
Chemical Science ( IF 7.6 ) Pub Date : 2024-09-09 , DOI: 10.1039/d4sc03396e
Jin Xiong ₁ , Christopher Reed ₂ , Barbara Lavina _{3,

4} , Michael Y Hu ₃ , Jiyong Zhao ₃ , Esen E Alp ₃ , Theodor Agapie ₂ , Yisong Guo ₁

Affiliation

⁵⁷ Fe nuclear resonance vibrational spectroscopy (NRVS) has been applied to study a series of tetranuclear iron ([Fe₄]) clusters based on a multidentate ligand platform (L³⁻) anchored by a 1,3,5-triarylbenzene linker and pyrazolate or (tertbutylamino)pyrazolate ligand (PzNH^tBu⁻). These clusters bear a terminal Fe(III)–O/OH moiety at the apical position and three additional iron centers forming the basal positions. The three basal irons are connected with the apical iron center via a μ₄-oxido ligand. Detailed vibrational analysis via density functional theory calculations revealed that strong NRVS spectral features below 400 cm⁻¹ can be used as an oxidation state marker for the overall [Fe₄] cluster core. The terminal Fe(III)–O/OH stretching frequencies, which were observed in the range of 500–700 cm⁻¹, can be strongly modulated (energy shifts of 20–40 cm⁻¹ were observed) upon redox events at the three remote basal iron centers of the [Fe₄] cluster without the change of the terminal Fe(III) oxidation state and its coordination environment. Therefore, the current study provides a quantitative vibrational analysis of how the remote iron centers within the same iron cluster exert exquisite control of the chemical reactivities and thermodynamic properties of the specific iron site that is responsible for small molecule activation.

中文翻译：

带有末端铁（III）-氧化/氢二基部分的四核铁簇的 57 Fe 核共振振动波谱研究

⁵⁷ Fe 核共振振动波谱（NRVS）已应用于研究一系列基于多齿配体平台（L³⁻）的四核铁（[Fe₄]）簇，该平台由 1,3,5-三芳基苯接头和吡唑酸盐或（叔丁氨基）吡唑酸盐配体（PzNH^tBu⁻）锚定。这些簇在顶端位置带有一个末端 Fe（III）-O/OH 部分，以及形成基部位置的三个额外的铁中心。三个基铁通过μ₄-氧化配体与顶铁中心连接。通过密度泛函理论计算进行的详细振动分析表明，低于 400 ^cm-1 的强 NRVS 光谱特征可以用作整个 [Fe₄] 团簇核心的氧化态标记。在 500-700 ^cm-1 范围内观察到的末端 Fe（III）-O/OH 拉伸频率可以在 [Fe₄] 簇的三个远程基铁中心的氧化还原事件中被强烈调制（观察到 20-40 ^cm-1 的能量转移），而末端 Fe（III 没有变化）氧化态及其配位环境。因此，目前的研究提供了对同一铁簇内的远程铁中心如何对负责小分子活化的特定铁位点的化学反应性和热力学性质进行精细控制的定量振动分析。

更新日期：2024-09-09

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