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Spin‐Controlled Binding of Carbon Dioxide by an Iron Center: Insights from Ultrafast Mid‐Infrared Spectroscopy
Angewandte Chemie International Edition ( IF 16.6 ) Pub Date : 2020-10-06 , DOI: 10.1002/anie.202012739
Steffen Straub 1 , Peter Vöhringer 1
Affiliation  

The influence of the spin on the mode of binding between carbon dioxide (CO2) and a transition‐metal (TM) center is an entirely open question. Herein, we use an iron(III) oxalato complex with nearly vanishing doublet–sextet gap, and its ultrafast photolysis, to generate TM‐CO2 bonding patterns and determine their structure in situ by femtosecond mid‐infrared spectroscopy. The formation of the nascent TM‐CO2 species according to [L4FeIII(C2O4)]+ + → [L4Fe(CO2)]+ + CO2, with L4=cyclam, is evidenced by the coincident appearance of the characteristic asymmetric stretching absorption of the CO2‐ligand between 1600 cm−1 and 1800 cm−1 and that of the free CO2‐co‐fragment near 2337 cm−1. On the high‐spin surface (S=5/2), the product complex features a bent carbon dioxide radical anion ligand that is O‐“end‐on”‐bound to the metal. In contrast, on the intermediate‐spin and low‐spin surfaces, the product exhibits a “side‐on”‐bound, bent carbon dioxide ligand that has either a partial open‐shell (for S=3/2) or fully closed‐shell character (for S=1/2).

中文翻译:

铁中心对二氧化碳的自旋控制结合:超快中红外光谱的见解

自旋对二氧化碳(CO 2)与过渡金属(TM)中心之间的结合方式的影响是一个完全开放的问题。在本文中,我们使用具有几乎消失的双峰-双键间隙的草酸铁(III)配合物及其超快光解作用,生成飞秒CO- 2键合模式并通过飞秒中红外光谱法原位确定其结构。根据[L 4 Fe III(C 2 O 4)] + + →[L 4 Fe(CO 2)] + + CO 2形成新生的TM-CO 2物种,其中L 4= cyclam,可以通过同时出现1600 cm -1和1800 cm -1之间的CO 2配体和2337 cm -1附近的游离CO 2的共同碎片的不对称拉伸吸收来证明。在高旋转表面(S = 5/2)上,产物配合物具有弯曲的二氧化碳自由基阴离子配体,该配体与金属呈O-“端对端”结合。相反,在中旋和低旋表面上,该产品表现出“侧向”结合的弯曲二氧化碳配体,该配体具有部分开壳(对于S = 3/2)或完全闭合外壳字符(对于S = 1/2)。
更新日期:2020-10-06
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