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

doi:10.1021/acs.organomet.7b00603

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 journal › Article › Research › peer-review

10 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 language	English
Pages (from-to)	761-771
Number of pages	11
Journal	Organometallics
Volume	37
Issue number	5
DOIs	https://doi.org/10.1021/acs.organomet.7b00603
Publication status	Published - 12 Mar 2018
Externally published	Yes

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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.",

author = "Kyne, {Sara H.} and Martin Cl{\'e}mancey and Genevi{\`e}ve Blondin and Etienne Derat and Louis Fensterbank and Anny Jutand and Guillaume Lef{\`e}vre and Cyril Ollivier",

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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 journal › Article › Research › peer-review

TY - JOUR

T1 - Elucidating Dramatic Ligand Effects on SET Processes

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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

PY - 2018/3/12

Y1 - 2018/3/12

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AB - 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

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