The Effect of trans Axial Isocyanide Ligands on Iron(II) Tetra-NHC Complexes and their Reactivity in Olefin Epoxidation

Eva Maria H.J. Esslinger; Jonas F. Schlagintweit; Greta G. Zámbó; Alexander M. Imhof; Robert M. Reich; Fritz E. Kühn

doi:10.1002/ajoc.202100487

The Effect of trans Axial Isocyanide Ligands on Iron(II) Tetra-NHC Complexes and their Reactivity in Olefin Epoxidation

Eva Maria H.J. Esslinger
, Jonas F. Schlagintweit
, Greta G. Zámbó
, Alexander M. Imhof
, Robert M. Reich
, Fritz E. Kühn

Associate Professorship of Molecular Catalysis

Technical University of Munich

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

The performance of trans axially substituted mono-(2 a) and bis(tert-butylisocyanide) (2 b) complexes derived from the highly active bio-inspired iron(II) (pre-)catalyst 2 containing an equatorial macrocyclic tetra N-heterocyclic carbene in homogenous olefin epoxidation catalysis is reported. H₂O₂ is used as oxidant in combination with the Lewis acid Sc(OTf)₃ as additive resulting in a considerable improvement of catalytic activity. In contrast to other iron epoxidation catalysts, the introduction of π-accepting isocyanide ligands does not improve the catalytic performance of 2 a and 2 b posed by cyclic voltammetry. However, besides their lower activity, a high temperature tolerance of both compounds is found as a unique feature for iron NHC epoxidation catalysts.

Original language	English
Pages (from-to)	2654-2662
Number of pages	9
Journal	Asian Journal of Organic Chemistry
Volume	10
Issue number	10
DOIs	https://doi.org/10.1002/ajoc.202100487
State	Published - Oct 2021

Keywords

N-heterocyclic carbenes
homogeneous catalysis
isocyanide ligands
non-heme iron complexes
olefin epoxidation

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10.1002/ajoc.202100487

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title = "The Effect of trans Axial Isocyanide Ligands on Iron(II) Tetra-NHC Complexes and their Reactivity in Olefin Epoxidation",

abstract = "The performance of trans axially substituted mono-(2 a) and bis(tert-butylisocyanide) (2 b) complexes derived from the highly active bio-inspired iron(II) (pre-)catalyst 2 containing an equatorial macrocyclic tetra N-heterocyclic carbene in homogenous olefin epoxidation catalysis is reported. H2O2 is used as oxidant in combination with the Lewis acid Sc(OTf)3 as additive resulting in a considerable improvement of catalytic activity. In contrast to other iron epoxidation catalysts, the introduction of π-accepting isocyanide ligands does not improve the catalytic performance of 2 a and 2 b posed by cyclic voltammetry. However, besides their lower activity, a high temperature tolerance of both compounds is found as a unique feature for iron NHC epoxidation catalysts.",

keywords = "N-heterocyclic carbenes, homogeneous catalysis, isocyanide ligands, non-heme iron complexes, olefin epoxidation",

author = "Esslinger, \{Eva Maria H.J.\} and Schlagintweit, \{Jonas F.\} and Z{\'a}mb{\'o}, \{Greta G.\} and Imhof, \{Alexander M.\} and Reich, \{Robert M.\} and K{\"u}hn, \{Fritz E.\}",

note = "Publisher Copyright: {\textcopyright} 2021 The Authors. Asian Journal of Organic Chemistry published by Wiley-VCH GmbH",

year = "2021",

month = oct,

doi = "10.1002/ajoc.202100487",

language = "English",

volume = "10",

pages = "2654--2662",

journal = "Asian Journal of Organic Chemistry",

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TY - JOUR

T1 - The Effect of trans Axial Isocyanide Ligands on Iron(II) Tetra-NHC Complexes and their Reactivity in Olefin Epoxidation

AU - Esslinger, Eva Maria H.J.

AU - Schlagintweit, Jonas F.

AU - Zámbó, Greta G.

AU - Imhof, Alexander M.

AU - Reich, Robert M.

AU - Kühn, Fritz E.

PY - 2021/10

Y1 - 2021/10

N2 - The performance of trans axially substituted mono-(2 a) and bis(tert-butylisocyanide) (2 b) complexes derived from the highly active bio-inspired iron(II) (pre-)catalyst 2 containing an equatorial macrocyclic tetra N-heterocyclic carbene in homogenous olefin epoxidation catalysis is reported. H2O2 is used as oxidant in combination with the Lewis acid Sc(OTf)3 as additive resulting in a considerable improvement of catalytic activity. In contrast to other iron epoxidation catalysts, the introduction of π-accepting isocyanide ligands does not improve the catalytic performance of 2 a and 2 b posed by cyclic voltammetry. However, besides their lower activity, a high temperature tolerance of both compounds is found as a unique feature for iron NHC epoxidation catalysts.

AB - The performance of trans axially substituted mono-(2 a) and bis(tert-butylisocyanide) (2 b) complexes derived from the highly active bio-inspired iron(II) (pre-)catalyst 2 containing an equatorial macrocyclic tetra N-heterocyclic carbene in homogenous olefin epoxidation catalysis is reported. H2O2 is used as oxidant in combination with the Lewis acid Sc(OTf)3 as additive resulting in a considerable improvement of catalytic activity. In contrast to other iron epoxidation catalysts, the introduction of π-accepting isocyanide ligands does not improve the catalytic performance of 2 a and 2 b posed by cyclic voltammetry. However, besides their lower activity, a high temperature tolerance of both compounds is found as a unique feature for iron NHC epoxidation catalysts.

KW - N-heterocyclic carbenes

KW - homogeneous catalysis

KW - isocyanide ligands

KW - non-heme iron complexes

KW - olefin epoxidation

UR - https://www.scopus.com/pages/publications/85114087894

U2 - 10.1002/ajoc.202100487

DO - 10.1002/ajoc.202100487

M3 - Article

AN - SCOPUS:85114087894

SN - 2193-5807

VL - 10

SP - 2654

EP - 2662

JO - Asian Journal of Organic Chemistry

JF - Asian Journal of Organic Chemistry

IS - 10

ER -

The Effect of trans Axial Isocyanide Ligands on Iron(II) Tetra-NHC Complexes and their Reactivity in Olefin Epoxidation

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Keywords

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