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

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

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",

year = "2018",

month = mar,

day = "12",

doi = "10.1021/acs.organomet.7b00603",

language = "English",

volume = "37",

pages = "761--771",

journal = "Organometallics",

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TY - JOUR

T1 - Elucidating Dramatic Ligand Effects on SET Processes

T2 - Iron Hydride versus Iron Borohydride Catalyzed Reductive Radical Cyclization of Unsaturated Organic Halides

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

N2 - 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.

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.

UR - https://www.scopus.com/pages/publications/85043589257

U2 - 10.1021/acs.organomet.7b00603

DO - 10.1021/acs.organomet.7b00603

M3 - Article

AN - SCOPUS:85043589257

SN - 0276-7333

VL - 37

SP - 761

EP - 771

JO - Organometallics

JF - Organometallics

IS - 5

ER -

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

Abstract

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