Development of (NO)Fe(N2S2) as a Metallodithiolate Spin Probe Ligand: A Case Study Approach,Accounts of Chemical Research

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Development of (NO)Fe(N2S2) as a Metallodithiolate Spin Probe Ligand: A Case Study Approach
Accounts of Chemical Research ( IF 16.4 ) Pub Date : 2024-02-28 , DOI: 10.1021/acs.accounts.3c00667
Manuel Quiroz ₁ , Marcetta Y Darensbourg ₁

Affiliation

The ubiquity of sulfur–metal connections in nature inspires the design of bi- and multimetallic systems in synthetic inorganic chemistry. Common motifs for biocatalysts developed in evolutionary biology include the placement of metals in close proximity with flexible sulfur bridges as well as the presence of π-acidic/delocalizing ligands. This Account will delve into the development of a (NO)Fe(N₂S₂) metallodithiolate ligand that harnesses these principles. The Fe(NO) unit is the centroid of a N₂S₂ donor field, which as a whole is capable of serving as a redox-active, bidentate S-donor ligand. Its paramagnetism as well as the ν(NO) vibrational monitor can be exploited in the development of new classes of heterobimetallic complexes. We offer four examples in which the unpaired electron on the {Fe(NO)}⁷ unit is spin-paired with adjacent paramagnets in proximal and distal positions.

中文翻译：

(NO)Fe(N2S2) 作为金属二硫醇盐自旋探针配体的开发：案例研究方法

自然界中普遍存在的硫-金属连接激发了合成无机化学中双金属和多金属系统的设计。进化生物学中开发的生物催化剂的常见主题包括将金属放置在靠近柔性硫桥的位置以及π-酸性/离域配体的存在。本报告将深入研究利用这些原理的 (NO)Fe(N ₂ S ₂ ) 金属二硫醇配体的开发。 Fe(NO) 单元是 N ₂ S ₂供体场的质心，其作为一个整体能够充当氧化还原活性、双齿 S 供体配体。它的顺磁性以及 ν(NO) 振动监测器可用于开发新型异质双金属配合物。我们提供了四个示例，其中 {Fe(NO)} ⁷单元上的不成对电子与近端和远端位置的相邻顺磁体自旋配对。

更新日期：2024-02-28

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