Elucidating Dramatic Ligand Effects on SET Processes: Iron Hydride versus Iron Borohydride Catalyzed Reductive Radical Cyclization of Unsaturated Organic Halides,Organometallics

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Elucidating Dramatic Ligand Effects on SET Processes: Iron Hydride versus Iron Borohydride Catalyzed Reductive Radical Cyclization of Unsaturated Organic Halides
Organometallics ( IF 2.5 ) Pub Date : 2017-09-27 00:00:00 , DOI: 10.1021/acs.organomet.7b00603
Sara H. Kyne ₁ , Martin Clémancey ₂ , Geneviève Blondin ₂ , Etienne Derat ₁ , Louis Fensterbank ₁ , Anny Jutand ₃ , Guillaume Lefèvre ₄ , Cyril Ollivier ₁

Affiliation

An iron(II) borohydride complex ([(η¹-H₃BH)FeCl(NCCH₃)₄]) is employed as the precatalyst in iron-catalyzed radical cyclizations of unsaturated organic halides in the presence of NaBH₄. Mechanistic investigations have established that the ligand bound to the metal center (acetonitrile versus ethylenebis(diphenylphosphine) (dppe)) plays a crucial role in the structure and reactivity of the active anionic iron(I) hydride ([HFeCl(dppe)₂]⁻) and borohydride ([(η¹-H₃BH)FeCl(NCCH₃)₄]⁻) with unsaturated haloacetals. This work provides new insights into iron(I) hydride and borohydride species and their potential implication in single-electron processes.

中文翻译：

阐明对SET工艺的显着配体影响：氢化铁与硼氢化铁催化不饱和有机卤化物的还原性自由基环化反应

铁（II）的硼氢化络合物（[（η ¹ -H ₃ BH）的FeCl（NCCH ₃）₄ ]）被用作在将NaBH的存在的不饱和有机卤化物的铁-催化的自由基环化预催化剂₄。机理研究表明，与金属中心键合的配体（乙腈与亚乙基双（二苯基膦）（dppe））在活性阴离子氢化铁（I）（[HFeCl（dppe）₂ ] ^-）和硼氢化钠（[（η ¹ -H ₃ BH）的FeCl（NCCH ₃）₄ ] ^-）与不饱和卤缩醛。这项工作为氢化铁（I）和硼氢化物种类及其在单电子过程中的潜在影响提供了新的见解。

更新日期：2018-02-02

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