Elucidating Dramatic Ligand Effects on SET Processes

Iron Hydride versus Iron Borohydride Catalyzed Reductive Radical Cyclization of Unsaturated Organic Halides

Sara H. Kyne, Martin Clémancey, Geneviève Blondin, Etienne Derat, Louis Fensterbank, Anny Jutand, Guillaume Lefèvre, Cyril Ollivier

Research output: Contribution to journalArticleResearchpeer-review

5 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)761-771
Number of pages11
JournalOrganometallics
Volume37
Issue number5
DOIs
Publication statusPublished - 12 Mar 2018
Externally publishedYes

Cite this

Kyne, Sara H. ; Clémancey, Martin ; Blondin, Geneviève ; Derat, Etienne ; Fensterbank, Louis ; Jutand, Anny ; Lefèvre, Guillaume ; Ollivier, Cyril. / Elucidating Dramatic Ligand Effects on SET Processes : Iron Hydride versus Iron Borohydride Catalyzed Reductive Radical Cyclization of Unsaturated Organic Halides. In: Organometallics. 2018 ; Vol. 37, No. 5. pp. 761-771.
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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.",
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Elucidating Dramatic Ligand Effects on SET Processes : Iron Hydride versus Iron Borohydride Catalyzed Reductive Radical Cyclization of Unsaturated Organic Halides. / Kyne, Sara H.; Clémancey, Martin; Blondin, Geneviève; Derat, Etienne; Fensterbank, Louis; Jutand, Anny; Lefèvre, Guillaume; Ollivier, Cyril.

In: Organometallics, Vol. 37, No. 5, 12.03.2018, p. 761-771.

Research output: Contribution to journalArticleResearchpeer-review

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AU - Kyne, Sara H.

AU - Clémancey, Martin

AU - Blondin, Geneviève

AU - Derat, Etienne

AU - Fensterbank, Louis

AU - Jutand, Anny

AU - Lefèvre, Guillaume

AU - Ollivier, Cyril

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