Fe-Based Complexes as Styrene Aziridination Catalysts: Ligand Substitution Tunes Catalyst Activity

Article abstract of DOI:10.1002/cctc.201901211

As part of our effort to improve our understanding of aziridination mechanism, we used tetra substitution of a diphenol ligand to modify the redox properties of corresponding Fe complexes. This allowed us to confirm that aziridination catalysis by Fe-base

Full text of DOI:10.1002/cctc.201901211

Accepted Article
Title: Fe-based complexes as styrene aziridination catalysts:
ligand substitution tunes catalyst activity
Authors: Guillaume Coin, Ranjan Patra, Martin Clémancey, Patrick
Dubourdeaux, Jacques Pécaut, Colette Lebrun, Ludovic
Castro, Pascale Maldivi, Sylvie Chardon-Noblat, and Jean-
Marc Latour
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemCatChem 10.1002/cctc.201901211
Link to VoR: http://dx.doi.org/10.1002/cctc.201901211
A Journal of
www.chemcatchem.org

ChemCatChem
10.1002/cctc.201901211
COMMUNICATION
Fe-based complexes as styrene aziridination catalysts:
ligand substitution tunes catalyst activity
ab$&
acd&
a
a
c
Guillaume Coin,
Ranjan Patra,
Martin Clémancey, Patrick Dubourdeaux, Jacques Pécaut,
c
c
c
b*
a*
Colette Lebrun, Ludovic Castro, Pascale Maldivi, Sylvie Chardon-Noblat, Jean-Marc Latour
Dedication ((optional))
[
19]
Abstract: As part of our effort to improve our understanding of
aziridination mechanism, we used tetra substitution of a diphenol
ligand to modify the redox properties of corresponding Fe complexes.
This allowed us to confirm that aziridination catalysis by Fe-based
complexes is governed by electron affinity of the active species and
dominated by radical delocalization
by polarity effects, the active species being either
or instead governed
[
21,24]
[15]
electrophilic
or nucleophilic.
We reported recently a combined experimental and
computational mechanistic study of aziridination using Fe
phenolate catalysts. The most active catalyst studied was the
III
II
further show that it correlates with the Fe /Fe redox potential.
III
II
[26,27]
dinuclear Fe Fe compound (1)
II
that was compared to
the mono Fe complex L Fe (MeCN) (Scheme 1). These
II
Cl
2
Nitrene transfer reactions have emerged in the past decade
as a general and efficient tool to synthesize various kinds of
kinds of mono Fe complexes were known for their versatility
and easy tunability and had been previously used for various
[
1]
amines,
the nitrene being generated by metal
[28–36]
catalytic reactions.
Our study disclosed that, for (1) and
decomposition of a precursor. A strong research effort is
currently devoted to replacing second row metal-based (i.e.
Cl
L Fe (MeCN)
II
2
, the aziridination reaction (Scheme 2) is
governed essentially by the electron affinity (EA) of the high-
IV
valent Fe imido active species which is best described as
[
Rh ) catalysts by more ecofriendly first row transition
2]
[
3–6]
[7]
metals,
and in particular iron.
A favored way to
Cl
L Fe - NTs
III
•
[14]
.
EA manifests in promoting in the transition
achieving this goal aims at elucidating mechanistic aspects
of the reaction by in-depth integrated experimental and
calculational studies. This was done in particular for
state a partial electron transfer from the olefin to the Fe-
bound tosylnitrene, a feature consistent with the moderately
negative slope of Hammett-like correlations.
[
8,9]
[8–11]
sulfimidation
and amination
by a few Fe reference
systems. However, a comparable understanding has not yet
[
Solv
O
Solv
FeII
12,13]
been attained for aziridination
[
in spite of recent such
Aziridines are interesting not only as
O
14–16]
R
R
N
studies.
A
B
-
N
2
ClO
4
pharmaceutical targets but also as useful synthetic
intermediates through easy opening of their three-membered
ring. Many different kinds of Fe aziridination catalysts have
been developed over more than three decades. These
Cl
R
R
R
R
f)2
T
LRFe (Solv)
II
N N
FeIII
N N
Fe(O
2
S=MeCN,
O
NEt
3
THF, Py
Cl
OH OH
FeII
O
Cl
Solvent
N
O
O
R
O
N
FeIII
[
17,18]
[19]
O
O
include heme-
[
and dipyrromethene-based
[20]
catalysts,
complexes,
R
R
N
R
N
N
15]
FeCl
3
linear
polyamine
and
21–24]
macrocyclic carbene
systems and even Fe salts.
tBu
H
H
H
2
2
2
L
: R = tBu
: R = Cl
: R = NO
[
[25]
Cl
L
L
Basic
(1)
R
R
NO2
2
LtBuFeIIICl
mechanistic features were studied thanks to a few Hammett
correlations. They revealed quite diverse behaviors
-
Cl
Cl
FeIII
O
O
R
R
N
N
[a]
Dr. G. Coin, Dr. R. Patra, Dr. M. Clémancey, Mr. P. Dubourdeaux,
Dr. J.-M. Latour
R
R
NH+
LRFeIIICl -
2 3
, Et
Univ. Grenoble Alpes, CEA, CNRS, IRIG, LCBM, 38000 Grenoble,
France,
Scheme 1. Schematic representation of diphenol ligands and complexes.
E-mail: jean-marc.latour@cea.fr
[
b]
c]
Dr. G. Coin, Dr. S. Chardon-Noblat
Univ. Grenoble Alpes, CEA, CNRS, DCM, 38000 Grenoble, France
E-mail: sylvie.chardon@univ.grenoble-alpes.fr
Dr. R. Patra, Dr. J. Pécaut, Mrs. C. Lebrun, Dr. L. Castro, Dr. P.
Maldivi
PhI=NTs
PhI
[
Univ. Grenoble Alpes, CEA, CNRS, IRIG, DIESE, SYMMES, 38000
Grenoble, France
LFeII
III •
LFe - NTs
[d]
Dr. R. Patra
Amity Institute of Click Chemistry Research & Studies (AICCRS)
Amity University, Sector-125, Noida, India
Present address: Department of Chemistry and Applied
Biosciences, ETH Zürich, 8093 Zürich, Switzerland
These authors contributed equally
Ts
N
$
&
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
II
Scheme 2. Fe -catalyzed aziridine formation.
This article is protected by copyright. All rights reserved.

ChemCatChem
10.1002/cctc.201901211
COMMUNICATION
However
[
the
prompted us to investigate further the above
mechanistic
variability
revealed
presence of triethylamine and were characterized by usual
methods (see below and SI). The X-ray structure of the ferric
15,24]
recently
Cl
III
phenolate system. Indeed, we reasoned that variation of the
ligand substitution should affect the electron affinity of the
active complex and thereby its catalytic efficiency. We have
complex
shows that the Fe ion is hexacoordinated by the
2 3
L Fe Cl (Et NH) was determined (Figure 1A). It
[ ]
III
NO2
L
donor set and two cis-chloro ligands, therefore leading to a
2 2
[N O ]
R
II
thus extended our series of ferrous L Fe (Solv)
x
complexes
CN, thf or pyridine
Scheme 1) to ligands with a strongly electron donating tBu
monoanionic species whose charge is balanced by a
III
R
II
R
(
(
(
R = tBu, Cl, NO
2
; x = 1 or 2; Solv = CH
3
x
triethylammonium cation. L Fe (Solv) and L Fe chlorido
complexes were also characterized in solution by UV-visible
(Figure 1B and Table S3) and Mössbauer (Figure S9 and
Table S3) spectroscopies, and electrochemistry (Table S3).
The Mössbauer spectra of ferrous compounds, recorded in
solution at 80 K, all appear as a quadrupole doublet. They
tBu
NO2
H
2
L
) and a strongly electron withdrawing NO
2
(
H
2
L
).
This tetranitro ligand had never been synthesized before.
The aziridination catalytic efficiencies were assessed and
gratifyingly, aziridination yields paralleled EAs of the
purported active species thus consolidating our initial
conclusion. To further investigate the ligand influence we
-
1
could be simulated with isomer shifts close to 1.15 mm s
-
1
and a quadrupole splitting in the range 2.0 - 3.3 mm s which
are indicative of high spin S=2 ions.
tBu
III
prepared
chlorido
mono
ferric
L
Fe Cl
and
R
L Fe Cl
III
2
(Et
3
NH) complexes (R = Cl or NO
2
, Scheme 1) and
The catalytic efficiencies of the four complexes were
evaluated at 25 °C in conditions identical to the mild ones
III
II
measured by cyclic voltammetry (CV) their Fe /Fe reduction
potentials. We found that aziridination yields correlate also
with these potentials. This strengthens the link between
aziridination activity and electronic properties and allows an
estimation of the catalytic ability of a given system.
[
14]
used in our previous report (Table 1).
In particular
acetonitrile was selected as solvent for increased catalyst
solubility and higher conversion. The yields obtained after 8
h
reaction indicate that aziridination by mononuclear
R
II
The tBu- and Cl-substituted ligands (Scheme 1) are
synthesized through a classical Mannich condensation,
complexes L Fe (NCMe)
withdrawing groups of the ligand R = tBu (5 %) < Cl (17 %) <
NO (31 %). But they are largely outweighed by the binuclear
2
is favored by the electron
NO2
which is not possible for
H
2
L
. We thus devised a three-
2
step synthetic route from 3,5-dinitrosalicylaldehyde (Scheme
S1) allowing one to obtain it as a yellow powder in 80 %
catalyst (1) (89 %). Conversely we found that aziridination is
favored by electrodonating substituents on styrene. Indeed
NO2
NO2
II
overall yield. The increased acidity of
H
2
L
, brought about
by the four nitro groups, was evidenced by its X-ray structure
competitive aziridinations run with
a yield (Y ) increase from p-CN to p-OMe (Table S7).
Moreover the log(Y /Y ) data could be linearly correlated to
parameter accounting for inductive and resonance
effects of substituents (Figure S11). A moderately negative
L
2
Fe (NCMe) showed
X
(
Figure
NO2
S7)
given
that
it
crystallized
as
X
H
+
[ EtNH] where the two phenols are
deprotonated and participate in a H-bond network.
L
H(H
2
O)][(iPr)
2
the s
+
value of the slope (r = -0.38) of the correlation indicates an
electrophilic active species (see below) and a partial charge
transfer in the transition state consistent with our previous
A
(b)
C
Cl
[14]
studies of
2
H L ligand.
[
a]
Table 1. Catalytic aziridination of styrene and catalysts properties.
cat. (5 mol %)
N
PhI=NTs
Ts
CH3CN, r.t.
B
R
II
tBu
Cl
NO2
Precatalyst L Fe (NCCH
3
)
2
L
L
L
(1)
89
[
b]
Aziridination yield (%)
5
17
31
R
III
•
[c]
EA of L Fe - NTs
110
-0.89
124
127
143
E (VAg/Ag+
)
III
II
R
III
[
d]
E(Fe /Fe ) of L Fe chlorides
-0.64
-0.34
Cl
III
Figure 1. (A) X-ray structure of the complex [L Fe Cl
2
](Et
3
NH). For the sake
of clarity, hydrogen atoms are not shown, except that of the ammonium
countercation. (B) UV-vis. spectra of the ligand NO2 (red line),
(green line). (C) Cyclic
[a] Reaction conditions: Catalyst/PhI=NTs/styrene molar ratio 0.05/1/10,
1
H
2
L
3
CH CN, 25 °C. [b] Yield (±3 % vs PhI=NTs) determined by H-NMR
NO2
III
NO2
II
[
L
Fe Cl
2
](Et
3
NH) (blue line) and
L
Fe (Py)
2
spectroscopy of crude reaction mixtures using mesitylene as internal
tBu
III
R
III
-
voltammograms of 1 mM L Fe Cl (a) and [L Fe Cl
2
] R = Cl (b) and NO
CN + 0.1 M TBAP (v = 100 mV s on VC electrode diam. 3 mm, reference
electrode Ag/Ag(NO ) 0.01 M).
2
(c)
standard. No aziridine is formed in absence of catalyst. [c] DFT calculated
-
1
-1
in CH
3
values in kcal mol (Table S11). [d] in V vs Ag/AgNO
0.1 M TBAP.
3 3
(0.01 M) in CH CN +
3
R
II
R
III
L Fe (Solv)
were prepared according to published procedures by
x
and L Fe chlorido complexes (Scheme 1)
To substantiate this observation, we pursued DFT
calculations. Considering the previous studies on NTs
R
[14]
[31]
reaction of
H
2
L
ligand with Fe(OTf)
2
or FeCl
3
in
This article is protected by copyright. All rights reserved.

ChemCatChem
10.1002/cctc.201901211
COMMUNICATION
[
8,9,14,37]
-
transfer with Fe complexes,
we focused our modelling
of Cl in electrolyte solution was indeed evidenced by
detection of its oxidation peak after performing a one-
electron exhaustive reduction at -0.97 V.
IV
on the Fe -imido active species. As a matter of fact we
investigated their main molecular and thermodynamics
features when changing the substituent from tBu to Cl to
When diphenolates are substituted by four chlorines
Cl
(H L ), which have a moderate electron withdrawing
2
NO
2
. Geometry optimizations of the three active species in
Cl
L Fe Cl
III
-
quintet spin state (see SI) yielded very similar structures with
the three ligands (Figures 2 and S12 and Table S8).
Based on spin densities on Fe and NTs group (Table S8),
character, the
[
2
]
complex exhibits
a
quasi-
= 0.17
Fe Cl, chlorides are
reversible behavior (Epc = -0.64 V, Epa = -0.47 V,
D
E
p
tBu
III
V, Figure 1C (b)). As for the above
L
III
•
the electronic configuration is consistent with an Fe - NTs
IV
radical species rather than an Fe =NTs complex. A similar
released during the exhaustive one-electron reduction of the
NO2
solution. Finally, the
III
-
[
L
2
Fe Cl complex exhibits two
]
situation has been already observed in such high-valent Fe
[
close reversible reduction peaks at E1/2 = -0.34 and -0.57 V
(Figure 1C (c)). CV investigations with varying scan rates
8,9,14,38,39]
imido complexes.
three complexes are close to 1.9 Å, similarly to previous
The Fe-NTs distances in the
III
suggested that these two systems correspond to two Fe
species of very close structure which are not in equilibrium.
This result is consistent with Mössbauer spectroscopy which
III
•
studies of high spin Fe - NTs.
[14,38]
The EA were calculated
for the three active species. They are fully consistent with the
expected increase in electrophilicity from the tBu substituent
to the Cl and the nitro one (EA = 109.5, 123.7 and 126.3 kcal
III
NO2
III
-
showed two Fe species for
[
L
Fe Cl
(Figure S9). We have assigned the
reversible system at the less negative potential, to
2
]
but a single
NO2
II
species for
L
Fe (Py)
2
-
1
III/II
mol , respectively, see Table S9 for details). It is worth noting
that this matches perfectly the trend revealed by catalytic
studies.
Fe
[
NO2
III
-
[41,42]
L
Fe Cl
2
]
complex.
In conclusion, this cyclic
voltammetry study illustrates the strong influence of ligand
substitution on the electronic properties of the complexes.
To our delight, we observed also that the variation of the
III/II
catalytic efficiencies parallels the evolution of the Fe
R
reduction potential of L Fe chlorido complexes (Figure 3).
III
II
A similar effect was observed recently for Mn catalysts.
[23]
This finding highlights how ligand substitution tunes Fe
electronic properties and hence the overall activity of the
catalyst.
ꢀ
NO2
III •
Figure 2. Optimized geometries (B3LYP-D3/BS1) of L Fe - NTs. The two
phenol groups are oriented in front and on the left and the pyridine ligand in the
back. The H atoms are omitted for sake of simplicity.ꢀ
To strengthen this apparent correlation between EA of
catalyst and aziridination efficacy, we investigated the
R
electrochemical properties of L Fe chlorido complexes, the
III
II
oxidized counterparts of the Fe precursors. All of them
present at least a one-electron reductive process (Figure 1C
Figure 3. Correlation of the aziridination yield with (left) the electron affinity of
the purport L Fe chlorido complexes.
3
and S10) in the 0 to -0.9 V range in CH CN electrolyte
R
III
solution, in addition to two ligand-centered oxidation
III
processes (Figure S10). As already proposed for similar Fe
[
28,40]
complexes,
III/II
we assigned the reductive process to the
Fe one-electron reduction process. This assignment was
confirmed by performing exhaustive electrolyses at applied
This combined experimental and theoretical study thus
confirms our initial finding that EA of the active species plays
a major role on styrene aziridination by this family of Fe
phenolate complexes. Moreover, it shows that there is a
monotonous trend between EA and the aziridination yield
III/II
Fe reduction potentials. Strong differences in the shapes
of the cyclic voltammograms and in the values of the
R
III
reduction potential (Figure 1C) of L Fe chlorido complexes
were observed. They illustrate clearly the major influence of
the substitution of the phenolate ligand on the Fe electronic
properties.
(
mol ). In addition, a similar trend links aziridination yields to
Figure 3) which extends over a large EA range (> 30 kcal
-1
III/II
the Fe reduction potential of the catalyst precursor (Figure
3
). This illustrates that the aziridination capacity of the
tBu
III
The CV of
irreversible redox system, with a reduction peak at Epc = -
.89 V associated with an oxidation peak at Epa = -0.38 V on
L
Fe Cl complex (Figure 1C (a)) exhibits an
catalyst (i) reflects the intrinsic electronic properties of the
system and (ii) can be evaluated by cyclic voltammetry
experiments.
0
the reverse scan. This behavior indicates that the one-
electron reduction is associated to a chemical change which
was assigned to the release of chloride ions. The presence
In addition, this study was made possible by the
NO2ꢀ
introduction of
substituents. The influence of these substituents manifests
a
new ligand
H
2
L
with four nitro
This article is protected by copyright. All rights reserved.

ChemCatChem
10.1002/cctc.201901211
COMMUNICATION
2
[
6
042–2058.
13] C. Damiano, D. Intrieri, E. Gallo, Inorganica Chim. Acta 2018, 470, 51–
7.
in solid state and solution properties of the ligand and its Fe
complexes. We showed here that this substitution eventually
led to a substantial enhancement in catalytic performance for
olefin aziridination. The same kind of activity enhancement
can be anticipated for acidic catalysis involving Fe or other
[14] R. Patra, G. Coin, L. Castro, P. Dubourdeaux, M. Clémancey, J. Pécaut,
C. Lebrun, P. Maldivi, J.-M. Latour, Catal. Sci. Technol. 2017, 7, 4388–4400.
[
15] D. W. Crandell, S. B. Munoz III, J. M. Smith, M.-H. Baik, Chem. Sci. 2018,
9, 8542–8552.
16] S. B. Isbill, P. P. Chandrachud, J. L. Kern, D. M. Jenkins, S. Roy, ACS
Catal. 2019, 9, 6223–6233.
17] J. P. Mahy, G. Bedi, P. Battioni, D. Mansuy, J. Chem. Soc. Perkin Trans.
1988, 1517–1524.
[
34,43]
[
metals.
[
2
[
[
18] Y. Liu, C.-M. Che, Chem. Eur. J. 2010, 16, 10494–10501.
19] E. T. Hennessy, R. Y. Liu, D. A. Iovan, R. A. Duncan, T. A. Betley, Chem.
Experimental Section
Sci. 2014, 5, 1526–1532.
20] P. P. Chandrachud, H. M. Bass, D. M. Jenkins, Organometallics 2016,
5, 1652–1657.
21] P. Liu, E. L.-M. Wong, A. W.-H. Yuen, C.-M. Che, Org. Lett. 2008, 10,
275–3278.
22] M. F. Shehata, S. K. Ayer, J. L. Roizen, J. Org. Chem. 2018, 83, 5072–
081.
23] V. Bagchi, A. Kalra, P. Das, P. Paraskevopoulou, S. Gorla, L. Ai, Q.
Wang, S. Mohapatra, A. Choudhury, Z. Sun, et al., ACS Catal. 2018, 8, 9183–
206.
24] C. M. Anderson, A. M. Aboelenen, M. P. Jensen, Inorg. Chem. 2019, 58,
107–1119.
[25] A. C. Mayer, A.-F. Salit, C. Bolm, Chem. Commun. 2008, 5975–5977.
[
3
[
3
[
5
[
Experimental details are provided as supplementary information.
Acknowledgements
9
[
1
S. C.-N., P. M. and J.-M. L. thank the Labex ARCANE and
CBH-EUR-GS (ANR-17-EURE-0003) for partial funding.
This work was performed using HPC resources from GENCI-
CINES (Grant 2016-c2016087 648) and GENCI-IDRIS
[
[
26] F. Avenier, J.-M. Latour, Chem. Commun. 2004, 1544–1545.
27] E. Gouré, F. Avenier, P. Dubourdeaux, O. Sénèque, F. Albrieux, C.
Lebrun, M. Clémancey, P. Maldivi, J.-M. Latour, Angew. Chem. Int. Ed. 2014,
53, 1580–1584.
(
Grant 2017-A0020807648).
[
28] R. Viswanathan, M. Palaniandavar, T. Balasubramanian, T. Muthiah,
Inorg. Chem. 1998, 37, 2943–2951.
Conflict of interest
[29] S. Heidari, E. Safaei, A. Wojtczak, P. Cotic, A. Kozakiewicz, Polyhedron
2
[
013, 55, 109–116.
30] J. Farrell, J. A. Niconchuk, P. R. Renehan, C. S. Higham, E. Yoon, M. V.
Andrews, J. L. Shaw, A. Cetin, J. Engle, C. J. Ziegler, Dalton Trans. 2014, 43,
610–6613.
31] A. M. Reckling, D. Martin, L. N. Dawe, A. Decken, C. M. Kozak, J.
Organomet. Chem. 2011, 696, 787–794.
32] L. E. N. Allan, J. P. MacDonald, G. S. Nichol, M. P. Shaver,
Macromolecules 2014, 47, 1249–1257.
33] H. Schroeder, B. R. M. Lake, S. Demeshko, M. P. Shaver, M. Buback,
Macromolecules 2015, 48, 4329–4338.
34] M. Taherimehr, J. P. Cardoso Costa Serta, A. W. Kleij, C. J. Whiteoak,
P. P. Pescarmona, ChemSusChem 2015, 8, 1034–1042.
The authors declare no conflict of interest.
6
[
Keywords: aziridination • iron catalyst • DFT calculations • redox
[
properties • mechanism
[
[
[
[
1]
2]
3]
H. M. L. Davies, J. R. Manning, Nature 2008, 451, 417–424.
J. Roizen, M. Harvey, J. DuBois, Acc. Chem. Res. 2012, 45, 911–922.
L. Maestre, W. M. C. Sameera, M. Mar Diaz-Requejo, F. Maseras, P. J.
[
[
[
[
35] K. Zhu, M. P. Shaver, S. P. Thomas, Chem. Asian J. 2016, 11, 977–980.
36] K. Zhu, M. P. Shaver, S. P. Thomas, Chem. Sci. 2016, 7, 3031–3035.
37] E. J. Klinker, T. A. Jackson, M. P. Jensen, A. Stubna, G. Juhász, E. L.
Pérez, J. Am. Chem. Soc. 2013, 135, 1338–1348.
4] V. Bagchi, P. Paraskevopoulou, P. Das, L. Chi, Q. Wang, A. Choudhury,
[
J. S. Mathieson, L. Cronin, D. B. Pardue, T. R. Cundari, et al., J. Am. Chem.
Soc. 2014, 136, 11362–11381.
Bominaar, E. Münck, L. Que, Angew. Chem. Int. Ed. 2006, 45, 7394–7397.
38] E. R. King, E. T. Hennessy, T. A. Betley, J. Am. Chem. Soc. 2011, 133,
917–4923.
[
4
[
5]
Ed. Engl. 2013, 52, 5309–5313.
6] P. K. Kuijpers, J. I. van der Vlugt, P. Schneider, B. de Bruin, Chem. Eur.
J. 2017, 23, 13819–13829.
L.-M. Jin, X. Xu, H. Lu, X. Cui, L. Wojtas, X. P. Zhang, Angew. Chem. Int.
[
[
39] M. Jaccob, G. Rajaraman, Dalton Trans. 2012, 41, 10430–10439.
40] R. K. Dean, C. I. Fowler, K. Hasan, K. Kerman, P. Kwong, S. Trudel, D.
[
B. Leznoff, H.-B. Kraatz, L. N. Dawe, C. M. Kozak, Dalton Trans. 2012, 41,
806–4816.
[
[
7]
8]
S. M. Paradine, M. C. White, J. Am. Chem. Soc. 2012, 134, 2036–2039.
S. Kumar, A. S. Faponle, P. Barman, A. K. Vardhaman, C. V. Sastri, D.
4
[
[
41] n.d.
Kumar, S. P. de Visser, J. Am. Chem. Soc. 2014, 136, 17102–17115.
9] S. Hong, X. Lu, Y.-M. Lee, M. S. Seo, T. Ohta, T. Ogura, M. Clémancey,
P. Maldivi, J.-M. Latour, R. Sarangi, et al., J. Am. Chem. Soc. 2017, 139, 14372–
4375.
10] R. E. Cowley, N. A. Eckert, S. Vaddadi, T. M. Figg, T. R. Cundari, P. L.
Holland, J. Am. Chem. Soc. 2011, 133, 9796–9811.
11] M. J. T. Wilding, D. A. Iovan, A. T. Wrobel, J. T. Lukens, S. N. MacMillan,
K. M. Lancaster, T. A. Betley, J. Am. Chem. Soc. 2017, 139, 14757–14766.
12] A. Fingerhut, O. V. Serdyuk, S. B. Tsogoeva, Green Chem. 2015, 17,
42] K. Ambrose, K. N. Robertson, C. M. Kozak, Dalton Trans. 2019, 48,
[
6
[
248–6260.
43] K. A. Andrea, T. R. Brown, J. N. Murphy, D. Jagota, D. McKearney, C.
M. Kozak, F. M. Kerton, Inorg. Chem. 2018, 57, 13494–13504.
1
[
[
[
This article is protected by copyright. All rights reserved.

ChemCatChem
10.1002/cctc.201901211
COMMUNICATION
Entry for the Table of Contents
Layout 1:
COMMUNICATION
cat. (5 mol %)
PhI=NTs
N
Iron aminophenolates: aziridination
Ts
Dr. Guillaume Coin, Dr. Ranjan Patra, Dr.
Martin Clémancey, Dr. Jacques Pécaut,
Colette Lebrun, Dr. Ludovic Castro, Dr.
Pascale Maldivi, Dr. Sylvie Chardon-Noblat,*
Dr. Jean-Marc Latour*
III/II
CH3CN, r.t.
yields parallel the Fe reduction
potentials of the catalyst precursors
allowing to evaluate the aziridination
capacity of the catalyst by cyclic
voltammetry experiments.
R = NO
2
R = Cl
N
N
FeII
O
O
Page No. – Page No.
R
R
N
R = tBu
N
Fe-based complexes as styrene
aziridination catalysts: ligand substitution
tunes catalyst activity
R
R
[a]
Dr. G. Coin, Dr. R. Patra, Dr. M. Clémancey, Dr. J.-M. Latour
This article is protected by copyright. All rights reserved.