Atanu Banerjee , Allison E. Creek , Aramice Y.S. Malkhasian , Annette M. Joseph , Korine C. Lowes , William W. Brennessel , Andreas Omlor , Volker Schünemann , Priya Singh , Timothy A. Jackson , Ferman A. Chavez
{"title":"烯烃二氧合酶的结构和功能模型。","authors":"Atanu Banerjee , Allison E. Creek , Aramice Y.S. Malkhasian , Annette M. Joseph , Korine C. Lowes , William W. Brennessel , Andreas Omlor , Volker Schünemann , Priya Singh , Timothy A. Jackson , Ferman A. Chavez","doi":"10.1016/j.jinorgbio.2024.112718","DOIUrl":null,"url":null,"abstract":"<div><p>In this article, we report sterically-controlled iron sites based on non-chelating bulky imidazole ligands. Adding 6 equiv. of 1,2-dimethylimidazole (1,2-Me<sub>2</sub>Im) to Fe(OTf)<sub>2</sub>⋅2CH<sub>3</sub>CN affords the first example of a 5-coordinate imidazole‑iron complex ([Fe(1,2-Me<sub>2</sub>Im)<sub>5</sub>](OTf)<sub>2</sub>, <strong>1</strong>). The structure is distorted square pyramidal (τ<sub>5</sub> = 0.41). When an <sup><em>i</em></sup>Pr group is substituted for the methyl group at the 2-position on the imidazole (2-<sup><em>i</em></sup>Pr-1-MeIm), the 14-electron complex ([Fe(2-<sup><em>i</em></sup>Pr-1-MeIm)<sub>4</sub>](OTf)<sub>2</sub>, <strong>2</strong>) is obtained. This complex exhibits slightly distorted tetrahedral geometry (τ'<sub>4</sub> = 0.93) with four N-donors and serves as a 4-His iron structural model complex for carotenoid cleavage dioxygenases (CCD). The electronic structure of <strong>1</strong> and <strong>2</strong> were characterized by Mössbauer spectroscopy. Reactions of <strong>1</strong> and <strong>2</strong> with model olefin substrates (1-R-4-(1-methoxyprop-1-en-2-yl)benzene; R = Me or Br) in the presence of oxygen result in olefin cleavage yielding ketone and aldehyde products, although <strong>2</strong> yields more products than <strong>1</strong>. Support for a proposed reaction mechanism for <strong>2</strong> is offered from Density Functional Theory (DFT) calculations.</p></div>","PeriodicalId":364,"journal":{"name":"Journal of Inorganic Biochemistry","volume":"262 ","pages":"Article 112718"},"PeriodicalIF":3.8000,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A structural and functional model for alkene dioxygenases\",\"authors\":\"Atanu Banerjee , Allison E. Creek , Aramice Y.S. Malkhasian , Annette M. Joseph , Korine C. Lowes , William W. Brennessel , Andreas Omlor , Volker Schünemann , Priya Singh , Timothy A. Jackson , Ferman A. Chavez\",\"doi\":\"10.1016/j.jinorgbio.2024.112718\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>In this article, we report sterically-controlled iron sites based on non-chelating bulky imidazole ligands. Adding 6 equiv. of 1,2-dimethylimidazole (1,2-Me<sub>2</sub>Im) to Fe(OTf)<sub>2</sub>⋅2CH<sub>3</sub>CN affords the first example of a 5-coordinate imidazole‑iron complex ([Fe(1,2-Me<sub>2</sub>Im)<sub>5</sub>](OTf)<sub>2</sub>, <strong>1</strong>). The structure is distorted square pyramidal (τ<sub>5</sub> = 0.41). When an <sup><em>i</em></sup>Pr group is substituted for the methyl group at the 2-position on the imidazole (2-<sup><em>i</em></sup>Pr-1-MeIm), the 14-electron complex ([Fe(2-<sup><em>i</em></sup>Pr-1-MeIm)<sub>4</sub>](OTf)<sub>2</sub>, <strong>2</strong>) is obtained. This complex exhibits slightly distorted tetrahedral geometry (τ'<sub>4</sub> = 0.93) with four N-donors and serves as a 4-His iron structural model complex for carotenoid cleavage dioxygenases (CCD). The electronic structure of <strong>1</strong> and <strong>2</strong> were characterized by Mössbauer spectroscopy. Reactions of <strong>1</strong> and <strong>2</strong> with model olefin substrates (1-R-4-(1-methoxyprop-1-en-2-yl)benzene; R = Me or Br) in the presence of oxygen result in olefin cleavage yielding ketone and aldehyde products, although <strong>2</strong> yields more products than <strong>1</strong>. Support for a proposed reaction mechanism for <strong>2</strong> is offered from Density Functional Theory (DFT) calculations.</p></div>\",\"PeriodicalId\":364,\"journal\":{\"name\":\"Journal of Inorganic Biochemistry\",\"volume\":\"262 \",\"pages\":\"Article 112718\"},\"PeriodicalIF\":3.8000,\"publicationDate\":\"2024-08-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Inorganic Biochemistry\",\"FirstCategoryId\":\"99\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0162013424002423\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"BIOCHEMISTRY & MOLECULAR BIOLOGY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Inorganic Biochemistry","FirstCategoryId":"99","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0162013424002423","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"BIOCHEMISTRY & MOLECULAR BIOLOGY","Score":null,"Total":0}
A structural and functional model for alkene dioxygenases
In this article, we report sterically-controlled iron sites based on non-chelating bulky imidazole ligands. Adding 6 equiv. of 1,2-dimethylimidazole (1,2-Me2Im) to Fe(OTf)2⋅2CH3CN affords the first example of a 5-coordinate imidazole‑iron complex ([Fe(1,2-Me2Im)5](OTf)2, 1). The structure is distorted square pyramidal (τ5 = 0.41). When an iPr group is substituted for the methyl group at the 2-position on the imidazole (2-iPr-1-MeIm), the 14-electron complex ([Fe(2-iPr-1-MeIm)4](OTf)2, 2) is obtained. This complex exhibits slightly distorted tetrahedral geometry (τ'4 = 0.93) with four N-donors and serves as a 4-His iron structural model complex for carotenoid cleavage dioxygenases (CCD). The electronic structure of 1 and 2 were characterized by Mössbauer spectroscopy. Reactions of 1 and 2 with model olefin substrates (1-R-4-(1-methoxyprop-1-en-2-yl)benzene; R = Me or Br) in the presence of oxygen result in olefin cleavage yielding ketone and aldehyde products, although 2 yields more products than 1. Support for a proposed reaction mechanism for 2 is offered from Density Functional Theory (DFT) calculations.
期刊介绍：
The Journal of Inorganic Biochemistry is an established international forum for research in all aspects of Biological Inorganic Chemistry. Original papers of a high scientific level are published in the form of Articles (full length papers), Short Communications, Focused Reviews and Bioinorganic Methods. Topics include: the chemistry, structure and function of metalloenzymes; the interaction of inorganic ions and molecules with proteins and nucleic acids; the synthesis and properties of coordination complexes of biological interest including both structural and functional model systems; the function of metal- containing systems in the regulation of gene expression; the role of metals in medicine; the application of spectroscopic methods to determine the structure of metallobiomolecules; the preparation and characterization of metal-based biomaterials; and related systems. The emphasis of the Journal is on the structure and mechanism of action of metallobiomolecules.
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