Elucidating dramatic ligand effects on SET processes: iron hydride versus Iron borohydride catalyzed reductive radical cyclization of unsaturated organic halides

Kyne, Sara H. and Clémancey, Martin and Blondin, Geneviève and Derat, Etienne and Fensterbank, Louis and Jutand, Anny and Lefèvre, Guillaume and Ollivier, Cyril (2018) Elucidating dramatic ligand effects on SET processes: iron hydride versus Iron borohydride catalyzed reductive radical cyclization of unsaturated organic halides. Organometallics, 37 (5). pp. 761-771. ISSN 0276-7333

Full content URL: http://dx.doi.org/10.1021/acs.organomet.7b00603

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Abstract

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.

Additional Information:This article is part of the Organometallic Chemistry in Europe special issue
Keywords:Iron, Radical reaction, Electrochemistry
Subjects:F Physical Sciences > F160 Organic Chemistry
F Physical Sciences > F100 Chemistry
F Physical Sciences > F161 Organometallic Chemistry
Divisions:College of Science > School of Chemistry
ID Code:28930
Deposited On:15 Mar 2018 10:24

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