The structure of a one-electron oxidized Mn(III)-bis(phenolate)dipyrrin radical complex and oxidation catalysis control via ligand-centered redox activity

Article abstract of DOI:10.1039/c6dt02163h

The tetradentate ligand dppH₃, which features a half-porphyrin and two electron-rich phenol moieties, was prepared and chelated to manganese. The mononuclear Mn(iii)-dipyrrophenolate complex 1 was structurally characterized. The metal ion lies in a square pyramidal environment, the apical position being occupied by a methanol molecule. Complex 1 displays two reversible oxidation waves at 0.00 V and 0.47 V vs. Fc⁺/Fc, which are assigned to ligand-centered processes. The one-electron oxidized species 1⁺ SbF₆^- was crystallized, showing an octahedral Mn(iii) center with two water molecules coordinated at both apical positions. The bond distance analysis and DFT calculations disclose that the radical is delocalized over the whole aromatic framework. Complex 1⁺ SbF₆^- exhibits an S_tot = 3/2 spin state due to the antiferromagnetic coupling between Mn(iii) and the ligand radical. The zero field splitting parameters are D = 1.6 cm^-1, E/D = 0.18(1), gt = 1.99 and g_∥ = 1.98. The dication 1²⁺ is an integer spin system, which is assigned to a doubly oxidized ligand coordinated to a Mn(iii) metal center. Both 1 and 1⁺ SbF₆^- catalyze styrene oxidation in the presence of PhIO, but the nature of the main reaction product is different. Styrene oxide is the main reaction product when using 1, but phenylacetaldehyde is formed predominantly when using 1⁺ SbF₆^-. We examined the ability of complex 1⁺ SbF₆^- to catalyze the isomerization of styrene oxide and found that it is an efficient catalyst for the anti-Markovnikov opening of styrene oxide. The formation of phenylacetaldehyde from styrene therefore proceeds in a tandem E-I (epoxidation-isomerization) mechanism in the case of 1⁺ SbF₆^-. This is the first evidence of control of the reactivity for styrene oxidation by changing the oxidation state of a catalyst based on a redox-active ligand.

Full text of DOI:10.1039/c6dt02163h

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PAPER
a.
Received 00th January 20xx,
Structure of a one-electron oxidized Mn(III)-
bis(phenolate)dipyrrin Radical Complex and Oxidation Catalysis
Control via Ligand-centered Redox Activity.
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
a
b
a
a
a
a
b
L. Lecarme, L. Chiang, J. Moutet, N. Leconte, C. Philouze, O. Jarjayes, T. Storr and F.
a
Thomas*
3
The tetradentate ligand dppH , which features a half-porphyrin and two electron-rich phenol moieties was prepared and
chelated to manganese. The mononuclear Mn(III)-dipyrrophenolate complex 1 was structurally characterized. The metal
ion lies in a square pyramidal metal ion, the apical position being occupied by a methanol molecule. Complex 1 displays
+
two reversible oxidation waves at 0.00 V and 0.47 V vs. Fc /Fc, which are assigned to ligand-centered processes. The one-
+
-
electron oxidized species 1 SbF
6
was crystallized, showing an octahedral Mn(III) center with two water molecules
coordinated at both apical positions. The bond distance analysis and DFT calculations disclose that he radical is delocalized
+
-
over the whole aromatic framework. Complex 1 SbF
6
exhibits an (Stot = 3/2) spin state due to the antiferromagnetic
-
1
coupling between Mn(III) and the ligand radical. The zero field splitting parameters are D = 1.6 cm , E/D = 0.18(1), g
⊥
= 1.99
2
+
and g
Mn(III) metal center. Both 1 and 1 SbF
reaction product is different. Styrene oxide is the main reaction product when using 1, but phenylacetaldehyde is formed
∥
= 1.98. The dication 1 is an integer spin system, which is assigned to a doubly oxidized ligand coordinated to a
+
-
6
catalyze styrene oxidation in the presence of PhIO, but the nature of the main
+
-
+
-
6 6
predominantly when using 1 SbF . We examined the ability of complex 1 SbF to catalyze the isomerization of styrene
oxide and found that it is an efficient catalyst for the anti-Markovnikov opening of styrene oxide. The formation of
phenylacetaldehyde from styrene therefore proceeds in a tandem E-I (epoxidation-isomerization) mechanism in the case
+
-
of 1 SbF
6
. This is the first evidence of control of the reactivity for styrene oxidation by changing the oxidation state of a
catalyst based on a redox-active ligand.
metal depending on the conditions (solvent, temperature,
electronics of the ligand), as in several porphyrin
Introduction
[8,9]
complexes.
This concept currently drives considerable
The design of highly active catalysts employing earth-abundant
transition metal ions for oxygenation reactions is one of the
most active research fields in inorganic chemistry. Perhaps the
most extensively studied inorganic platforms for this purpose
are Mn(salen) (in particular Jacobsen’s catalyst, see Scheme
interest in catalysis since the redox-active organic framework
could potentially act as an electron reservoir during
[10]
turnover. Recent advances in this field have been achieved
[12]
[
11]
for [2+2] cycloadditions,
atom transfer reactions,
and
[13]
[
1]
alcohol oxidation. There are comparatively few examples of
redox non-innocent ligands that tune the reactivity of a
1) and Mn(porphyrin) complexes. In the generally accepted
mechanism the Mn(III) precatalyst reacts with an oxygen atom
donor (PhIO) to form a high-valent manganese oxo species (or
PhIO adduct), which is directly involved in the epoxidation
[14-15]
complex without participating in the electron transfer.
[2]
[3]
reaction. We and others established in related Mn(III),
[4]
[5]
[6]
[7]
Fe(III), Co(II), Cu(II), and Ni(II) salen complexes that the
ligand can be redox non-innocent when the phenol moieties
are functionalized by electron-donating groups. Thus, the
electronic hole can be located on the ligand instead of at the
N
O
N
O
Mn
X
N
O
N
O
t-Bu
t-Bu
Mn
X
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
Jacobsen's catalyst
X = CH
3
OH, 1
Scheme 1. Formula of the Jacobsen’s catalyst and 1
We recently reported on the coordination chemistry of a
bis(phenol)dipyrrin ligand, which incorporate tert-butyl groups
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[
16]
at both the ortho and para positions of the phenol moieties.
The manganese complex
1
was prepared by reacting dppH
O in the presence of NEt under
3
We established by combined X-Ray diffraction and and 2 equiv of Mn(OAc)
3
.2H
2
3
spectroscopy that the neutral nickel and cobalt complexes are an argon atmosphere, followed by exposure to air. The crystal
indefinitly stable Ni(II) and Co(II)-radical species. We herein structure of (Fig. 1A) displays a mononuclear complex, with a
1
extend this study to the manganese ion, with a newly designed manganese ion that lies in a square pyramidal geometry, in
ligand. While the phenol groups still harbour two tert-butyl which the O1, O2, N1, N2 atoms of the ligand defines the
substituents, which are essential to stabilize the high oxidation equatorial plane, and the apical position (O3) occupied by a
states of the complex, the dipyrrin is functionalized in meso methanol molecule. The coordination bond distances (Table 1)
[17]
position by a triaryl moiety. We envision that this new feature are indicative of a high spin Mn(III) ion. The Mn-O3 bond
will prevent the dimerization, as observed by Aukauloo et al. length of 2.270(4) Ǻ confirms that the methanol ligand is not
[
17]
[20]
in a related manganese complex, while keeping labile deprotonated upon coordination.
coordination sites essential for catalysis. bond lengths are 1.336(4) Ǻ and 1.332(5) Ǻ, respectively.
We establish that undergoes two oxidative redox processes, These values are similar to those reported for Mn -
producing the persistent radical species
The C1-O1 and C22-O2
III
1
+
1
2+
[17]
and the dication
1
.
bis(phenolato) complexes, attesting that the ligand is in its
+
We investigate the catalytic activity of both
styrene oxidation in the presence of PhIO.
1
and
1
for tri-anionic closed-shell electronic configuration. Furthermore,
DFT calculations accurately predict the coordination sphere
bond lengths (≤ 0.03 Å for the S = 2 state, see Table S2).
Results and discussion
+
and 1 SbF
-
Table 1. Selected bond lengths in
1
6
(from the crystal structures)
Synthesis of the ligand and characterization of 1
+
-
6
+
-
The ligand dppH
First, two
methoxyphenyl)pyrrole
3
was prepared following a two-step sequence.
equivalents of 2-(3,5-di-tert-butyl-2-
were condensed on 2,6-diphenyl Mn-N2
in the presence of trifluoroacetic acid.
1
1 SbF
1
1 SbF
6
Mn-N1
1.956(3)
1.963(3)
1.870(3)
1.857(3)
2.270(4)
-
1.955(7)
1.955(7)
1.868(7)
1.868(7)
2.295(6)
2.295(6)
O1-C1
C2-C3
C3-C4
C9-C10
C8-C9
C6-C7
1.336(4)
1.386(6)
1.394(6)
1.415(5)
1.369(6)
1.451(6)
1.304(13)
1.326(20)
1.442(20)
1.471(11)
1.298(12)
1.437(12)
[18]
[a]
[
19]
benzaldehyde
Mn-O1
[
a]
b]
b]
Subsequent oxidation with an equimolar amount of 2,3- Mn-O2
[
Mn-Oax
dichloro-4,5-dicyano-p-benzoquinone afforded the di-O-
[
Mn-Oax
methylated precursor dppHMe
2
in a 84% yield after
purification. Deprotection of the phenol moieties with sodium
a
+
-
N2 refers to N1* in 1 SbF
6
. Mn-Oax corresponds to one Mn-O3 bond in 1 (square
dodecylthiolate gave the targeted dppH
yield.
3
in a satisfactory 69%
+
-
6
pyramidal) and both Mn-O3 bonds in 1 SbF (octahedral).
Complex
1 was found to be EPR silent in CH Cl at 10 K. This
2 2
feature is reminiscent of complexes having an integer spin
ground state with zero field splitting (zfs) parameters larger
-1
than the X-Band energy quantum (≈ 0.3 cm ) and wherein the
[21]
symmetry in the zfs interaction is close to axial.
High spin
Mn(III) complexes are the archetype of such systems, which
are usually difficult to characterize by perpendicular X-band
[
21]
EPR spectroscopy.
Indeed, under these conditions the
Ms = ±1 transitions are not
conventional spin allowed ꢀ
possible since the energy required is much larger than 0.3 cm
-
1
.
+
-
Figure 1. X-Ray crystal structure of A)
1
and B)
1
SbF
6
at the 30 % ellipsoid
probability (H atoms omitted for clarity except those of the coordinated water
molecules).
2
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1
2
8
4
0
4
I / ꢁA
-
-
0.4
-0.2
0.0
0.2
0.4
0.6
E / V
Figure 3. Cyclic voltammetry curve of
1
in CH
2
-
Cl
2
(containing 0.1 M TBAP) at a
1
carbon electrode. T = 298 K. Scan rate = 0.1 V s
+
versus the Fc /Fc reference couple.
. The potential values are given
Bulk electrolysis at a controlled potential produces the cations
+ 2+
1 and 1 quantitatively, which were characterized by EPR and
+
2+
2 2
Figure 2. UV-Vis-NIR spectra of CH Cl solutions of 1 (black), 1 (red) and 1
(
blue). T = 298 K. The TD-DFT calculated transitions are indicated as vertical bars.
Vis-NIR spectroscopies.
+
1
The Vis-NIR spectrum of the electrochemically generated
differs markedly from that of the neutral precursor
1 (Fig. 2).
Spectro-electrochemistry
The electrochemical behavior of the ligand dppH
been investigated by cyclic voltammetry (CV). The CV curve of
in CH Cl (0.1 M TBAP solution) is characterized by two
reversible oxidation waves at E 1/2 = 0.00 V (
The most salient features are the attenuation of the main
transition at 730 nm and the appearance of several NIR
3
and 1 has
features that are indicative of the formation of a radical
2+
1
2
2
1
species (see below for details). The dication
1
also displays
ꢀ
E
p
= 0.097 V) and
2
+
intense NIR bands, but its spectrum is distinct from that of the
E
1/2 = 0.47 V (ꢀE = 0.104 V) vs. Fc /Fc (Fig 3). Both correspond
p
cation, suggesting the formation of a quinone-like species.
+
to one-electron redox couples and are assigned to ligand-
centered oxidation processes (see below). These potential
values are lower than those measured for the free ligand
The X-band EPR spectrum of
1
(Fig. 4) displays a set of
resonances at geff = 5.4, 2.9, 2 and <1.6, which are indicative of
an (Stot = 3/2) ground spin state of the complex. This spectrum
could be interpreted by considering either an
1
2
3
3 2 2
dppH in CH Cl (E 1/2 = 0.19 V, E 1/2 = 0.61 V and E 1/2 = 0.92
V), most likely because of the deprotonation of the oxygen
donors. Conversely, the first oxidation wave in the complex,
antiferromagnetic coupling between the ligand radical spin
[3,22,23]
2
-
3-
(Srad = ½) and the high spin Mn(III) centre (SMn = 2),
or
which corresponds to the dpp /dpp redox couple, is
anodically shifted by ca. 0.5 – 0.6 V in comparison to related
Ni(II) and Co(II) bis(phenolate)dipyrrin complexes (reduction
wave in these cases since the complexes were isolated under
3
alternatively by considering a d Mn(IV) ion coordinated to
[24]
closed-shell ligand.
spectroscopy and the solid state structure of
clearly rules out the latter formulation. Thus, complex 1 is a
However, both the UV-Vis-NIR
+
1
(see below)
+
[16]
their radical forms).
We interpret this shift by the higher
55
magnetically coupled Mn(III) radical species, and the Mn
hyperfine lines that are well resolved in the low field
formal charge at the metal center in the manganese case. The
2
1
ꢀ
E
1/2 value (
ꢀ
E
1/2 = E 1/2 – E 1/2) is 0.47 V, thus within the range
-1
-1
resonance (A
indicative of interaction between the radical and the metal
16] center. The following Spin Hamiltonian parameters were
⊥ ∥
= 0.008 cm and A = 0.005 cm ), are further
of those calculated for the Ni(II) and Co(II)
ox
red
bis(phenolate)dipyrrin complexes (
ꢀE1/2 = E 1/2 – E 1/2 in
[
these cases), which are ꢀ 1/2 = 0.51 and 0.60 V, respectively.
E
-1
obtained from simulation: D = 1.6 cm ; E/D = 0.18(1); g
⊥
= 1.99;
This analogy suggests similar assignment of the redox waves,
1
i.e. ligand-centered processes. It is interesting that the E1/2
∥
g = 1.98. Since the D value is larger than the X-band energy
quantum, it could be only roughly estimated and the value 1.6
-1
cm represents a lower limit.
value is lower for
1
than for the dinuclear manganese complex
[17]
reported by Aukauloo et al.
This shift likely results from
both the absence of tert-butyl groups in ortho and para
positions of the phenolate moieties, as well as the bridging
1
nature of the phenolato donors in their case (E1/2 = 0.67 V vs.
[17]
SCE in CH
3
CN).
Altogether, these data support ligand
participation in the redox processes.
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calculations at the B3LYP level of theory support this
assignment, by showing spin density distributed over the
metal center (3.91), and delocalized over both phenoxyl rings
(-0.24 and -0.28 each) and the dipyrrin framework (-0.59, Fig.
5
a). The (Stot = 3/2) spin state, due to antiferromagnetic
d
dB
χ
''
coupling between Mn(III) and the ligand radical, is correctly
-1
predicted to be the lowest in energy (2.9 kcal mol below the
Stot = 5/2 state).
*
1
00
200
300
400
500
600
B / mT
+
-
Figure 4. X-band EPR spectrum of a CH
Cl
2 2
solution of
1
SbF
6
(black lines) and
simulation using the parameters given in the text (red lines). T = 10 K. *: Impurity
in the cavity.
+
2+
In contrast to
Band EPR silent at 10 K in perpendicular mode (B
using a parallel polarization mode (B // B ), a resonance could
be easily detected at g = 8. This strongly supports an integer
1
the dication
1
was found to be mainly X-
0
_|_ 1
B
). By
0
1
2
1
+
ground spin state for
(Fig S4). According to the
[23,25]
literature,
this low field resonance is assigned to a
+ 5 2+
1 and (b) 1 .
Figure 5. Spin density plots for (a)
transition within the Ms = ±2 doublet of an (SMn = 2) Mn(III)
ion. It must be stressed that this spectrum is clearly different
2
+
[
26] The electronic structure of the dication
1
has been
than that reported for anilinyl-Mn(IV) radical complexes.
2
+
1 is consistently assigned to a high spin manganese(III)
investigated by DFT calculations, by considering two axially
5
Thus,
2+
bound water molecules (Fig 5b). Both the (S = 2) (
7
1
) and (S =
complex involving a doubly oxidized, and subsequently closed-
-
shell, ligand dpp .
2+
3) ( 1 ) spin states were calculated, but only the first is
relevant (more stable by 9.4 kcal mol ). The spin density is
-1
5
2+
1 , supporting a non-
mainly localized on the metal center in
Geometric and electronic structures of the oxidized species
radical character of the ligand. Thus, DFT calculations correctly
+
The monocation
using AgSbF
donor. Brown single crystals of 1 SbF
diffusion of pentane into a dichloromethane solution of the Vis-NIR spectroscopy and TD-DFT calculations
1
was synthesized on a preparative scale by predict the dication to be a high spin Mn(III) complexes
6
, i.e. a one-electron oxidant that is not an oxygen coordinated to a doubly-oxidized closed-shell ligand.
+
-
6
were grown by slow
2
1
+
complex. The dication
part due to its lower stability.
The X-ray crystal structure of 1 SbF
selected bon distances summarized in Table 1. The geometry
could not be isolated similarly, in
The manganese complex
1 exhibits distinct Vis-NIR spectra
depending on its oxidation state (Table 2).
+
-
6
is shown in Fig. 1B and
[
a]
Table 2. Vis-NIR spectroscopic data.
+
-
of the metal ion in 1 SbF
6
is octahedral, with two water
-1
-1
λ [nm] (ε [M cm ])
molecules that occupy the axial positions. We ruled out both
deprotonation of the axial ligands and the presence of a
Mn(IV) center since the Mn-O3 and Mn-O4 bond distances
would be much shorter than those experimentally measured
1
1
475 (13100), 675 sh (9110), 730 (20000), 955 (540), 1080 (560)
+
2
425 (12475), 455 (12575), 495 (12580), 515 (13430), 680 (5040), 720
(
4340), 945 (6710), 1060 sh (2950), 1390 (2860)
+
1
430 (14750), 520sh (8830), 560 sh (7000), 595 sh (5840), 715 (4405),
960 (4380), 1140 (6010), 1340 (7600)
(
2.295 Å): The expected bond lengths are indeed 1.67± 0.03 Å
IV
for a Mn =O core, and 1.839(2) Å for Mn -OH or Mn -OCH
IV
IV
[b]
3
2
417 (14 710), 507 (9520), 645 (6780), 934 (4360)
[3,27]
core.
Furthermore, each O3 atom resides at an H-bonding
-
a
Solvent: anhydrous CH
2
Cl
2
.
distance of an SbF
6
counter ion (shortest O3-F3 distance at
b
2.75 Å). Within the pyrrole ring the C8-C9 bond length
oxomanganyl species generated by adding 1.1 molar equivalent of PhI(OAc)
2
to 1,
see below.
decreases from 1.369(6) to 1.298(12) Å upon oxidation from
1
+
to
.471(11) Å. Further, the C2-C3 bond shortens from 1.386(6)
to 1.326(20) Å while the C3-C4 bond lengthens from 1.394(6)
to 1.442(20) upon oxidation. This bonding pattern
unambiguously shows that
featuring hybrid “phenoxyl-pyrroyl” radical.
1 , while the C9-C10 bond extends from 1.415(5) to
+
1
The Vis-NIR spectrum of the electrochemically generated
is
1
-1
-1
characterized by low energy bands at 1390 nm (2860 M cm ),
-1
-1
-1
060 (2950 M cm ) and 945 nm (6710 M cm ). In order to
-1
1
Å
+
gain insight into the nature of the NIR electronic transitions,
TD-DFT calculations were undertaken. Three NIR bands are
predicted, in agreement with the experimental spectra (Fig. 2
1
is a genuine Mn(III) complex
[16,28]
a
DFT
4
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and 6). The NIR band of highest intensity is predicted at
λ
calcd
=
aldehyde remained unchanged (Table 3, entry 2). It is
noteworthy that under anaerobic and anhydrous conditions
1
318 nm (fosc = 0.0583), and corresponds to a α-
α
-HOMO →
LUMO transition. From orbital composition analysis it is the epoxide formed in a slightly lower 19% yield (Table 3, entry
assigned to a phenoxyl → dipyrrin ligand-ligand charge transfer 3). Notwithstanding, we ruled out a role of dioxygen in the
transition (LLCT) (Fig. 6). The two other low energy bands are reaction since no reaction occurs in the absence of PhIO (Table
predicted at 1075 nm (fosc = 0.0263) and 858 nm (fosc = 0.0242) 3, entry 4).
+
-
and again correspond to CT transitions.
2
The catalytic properties of 1 SbF
6
were then investigated.
dramatically affected the
+
+
with 1 SbF
-
The dication
1
also displays intense NIR bands, but their Remarkably, replacing
1
6
intensities are distinct from those in the cation: 1340 nm (7600 product distribution of the reaction. Indeed, the reaction
+
-
1
-1
M cm ), 1140 nm (6010 M cm ) and 960 nm (4380 M cm between styrene and 1 equiv of PhIO in the presence of
-1
-1
-1
-
1
1
-
)
6
. The three lowest energy electronic excitations are SbF affords predominantly phenylacetaldehyde in 22% yield,
calculated at 1324 nm (fosc = 0.0296), 1191 nm (fosc = 0.0462) together with a small amount of benzaldehyde (Table 3, entry
and 1042 nm (fosc = 0.0223), showing again a good agreement 5). Unexpectedly, no epoxide was detected. As observed with
between theory and experiment. In this case numerous
1, a higher amount of PhIO had an inhibitory effect on catalysis
contributions from many sets of orbitals are involved (see ESI). (Table 3, entry 6), whereas the reaction outcome remains
unaffected under inert conditions (Table 3, entry 7). Thus, both
+
-
1
and 1 SbF are capable of oxygen insertion in the presence
6
+
-
of PhIO. However, only 1 SbF allows the anti-Markovnikov
6
oxidation (the addition does not occur through the formation
of the most substituted carbocation) of styrene into
phenylacetaldehyde. Changes in product distribution have
been reported for some catalysts based on manganese salan
complexes, but not to such an extend and for catalysts that
[29]
differ by their substituents instead of oxidation state.
+
and 1 SbF
- [a]
.
Table 3. Oxidation of styrene by
1
6
[
Mn] (1 mol%)
O
+
PhIO
CHO
+
O
CH2Cl2, rt
Epoxide
PhCH
2
CHO
PhCHO
Entry
[Mn]
PhIO
b
b
b
(%)
(%)
(%)
1
2
1
1
1
1
1
2
1
-
31
19
19
0
3
7
7
2
3
c
3
5
4
5
6
0
0
+
-
-
-
1 SbF
6
6
6
1
2
1
0
22
12
19
12
20
11
+
1 SbF
0
+
.
Figure 6. TD-DFT assignment of the calculated NIR transitions for
1
c
+
7
1 SbF
0
a
+
-
Conditions: Styrene (0.1 M), [Mn] complex (1 mM), PhIO (0.1 or 0.2 M), CH
2
Cl
2
(2
Catalytic activity of 1 and 1 SbF
6
towards styrene oxidation
b
mL), 25°C, 20h. Yields are the mean of 2 runs and were determined by GC analysis
-
2
c
Having established that the oxidation state of the ligand differs using biphenyl (5.10 M) as internal standard. Run performed under argon and
+
-
anhydrous conditions.
6
in 1 and 1 SbF , we examined the ability of both complexes to
oxidize styrene, a classical olefinic substrate, in the presence of
an oxygen atom donor (Table 3). Due to its low stability and
+
-
6
Catalytic activity of 1 SbF towards isomerization of styrene oxide
2
+
difficulties in isolating
1
at the solid state we refrained to In order to gain insight into this unique reactivity, we
+
-
extend the catalytic investigation to the dication. Thus,
1
6
(1 examined the ability of 1 SbF to catalyze the isomerization of
mol%) catalyzes the reaction between the olefinic substrate styrene oxide under air (Table 4). In the absence of PhIO
and a molar equivalent of iodosylbenzene to afford mainly phenylacetaldehyde was the sole product detected (Table 4,
styrene oxide in a 31% yield (31 turnovers, Table 3, entry 1). It entry 1). Repeating the reaction with 1 equiv of PhIO afforded
is worth noting that 10 turnovers were obtained for the a mixture of benzaldehyde (23 %) and phenylacetaldehyde (30
epoxidation of cyclooctene with the related manganese %) (Table 4, entry 2). In both cases the yield of
[
17]
described by Aukauloo et al.,
conditions. Trace amounts of phenylacetaldehyde and showing that
benzaldehyde were also detected. No reaction was observed Markovnikov isomerization of styrene oxide. The formation of
in the absence of
. Increasing the PhIO loading to 2 equiv led phenylacetaldehyde from styrene therefore proceeds in a
albeit with different phenylacetaldehyde was higher than in any other experiments,
+
-
1
6
SbF is an efficient catalyst for the anti-
1
to a decrease in the epoxide yield while the amount of
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DOI: 10.1039/C6DT02163H
PAPER
tandem E-I (epoxidation-isomerization) mechanism, where
Dalton Trans.
+
1
-
6
SbF acts as a bifunctional catalyst.
30
20
10
0
(
a)
+
- [a]
Table 4. Catalytic isomerization of styrene oxide by 1 SbF
6
.
1+ SbF -
(1 mol%)
Additive
6
O
O
CHO
+
+
O
2 2
CH Cl , rt
(
Phenyl-
Benzaldehyde
(%)
Acetophenone
(%)
Entry
Additive
acetaldehyde (%)
1
2
-
30
30
0
0
0
PhIO
400
600
800
1000
23
(
1 equiv)
λ (nm)
a
+
-
Conditions: Styrene oxide (0.1 M), 1 SbF
6
(1 mM), PhIO (0.1 M), CH
2
Cl
2
(1
mL), 25°C, 20h.
30
20
10
0
(
b)
+
-
Reactivity of 1 and 1 SbF
6
with oxygen atom donors
+
We next examined by spectroscopy the reactivity of
-
1
and
1
SbF
higher than that of PhIO. The addition of 1.1 eqt of PhI(OAc)
6 2
with PhI(OAc) , an oxygen atom donor whose solubility is
2
+
and 1 SbF
-
to
1
6
induces clean spectral changes, supporting a
transfer of an oxygen atom to the pre-catalyst, leading to the
adduct (Fig. 7, Table 2). After one hour no more significant
evolution is observed and the spectrum, whether the starting
2
+
-
material is
the case of
conversion of a related Mn(III) complex to its Mn(V)-oxo
1
or 1 SbF
6
, is identical. The evolution observed in
4
00
600
800
1000
1
is remarkably similar to that reported upon
λ (nm)
[
30]
counterpart.
Hence, it consists of transitions at 337
Figure 7. Spectral evolution after mixing
precatalysts with 1.1 molar eqt of PhI(OAc) at 302 K. (a)
indicate the spectral changes as a function of time (one spectrum each minute).
with Insert: ESI-MS profile after mixing with 10 molar eqts of PhI(OAc)
2 2
a CH Cl solution of the Mn(III)
(
(
18 265), 417 (14 710), 507 (9520), 645 (6780) and 934 nm
+
2
1 and (b) 1 . The arrows
-1
-1
4360 M cm ). Owing to its thermal stability, the species
2
could be characterized by ESI-MS. After mixing
PhI(OAc) the molecular peak of the initial material shifts by 16
units (m/z = 848.4), indicative of Mn(V)=O formation (Fig. 7, Thus, both
1
1
2
.
2
+
-
1
and 1 SbF
in the presence of PhIO. This oxomanganyl complex
donor was also monitored by EPR spectroscopy. The spectrum is the active oxygen atom donor responsible for styrene
remains silent in the case of
, confirming its conversion into a oxidation to styrene oxide. Its formation likely proceeds more
species having an integer spin system. After 20 min reaction of slowly with PhIO than with PhI(OAc) due to the limited
) the EPR solubility of the former. This suggests the simultaneous
6
are converted into an oxomanganyl
+
-
insert). The reaction of
1 and 1 SbF
6
with an oxygen atom species 2
1
2
+
-
PhIO with 1 SbF
6 2 2
at room temperature (in CH Cl
+
-
spectrum still exhibits the features of an (S = 3/2) system, but presence of both
the intensity is three times lower (Fig S7), consistent with its in solution, at least in the early stage of catalysis. The
slow conversion into an oxomanganyl species. Thus, these difference in the product distribution of the oxidation reaction
2
6
and the Mn(III) pre-catalyst (1 or 1 SbF )
+
-
spectroscopic data support a progressive conversion of both by
-
6
1 and 1 SbF can be rationalized by the relative Lewis
+
and 1 SbF
Mn(III) complexes (
species.
1
6
) into a high valent metal oxo acidity of the metal center modulated by the ligand oxidation
state. Under its trianionic closed-shell electronic configuration,
the ligand is a strong donor. The relatively weak Lewis acidity
at the metal center disfavours isomerization of the bound
+
[29]
-
6
epoxide. In 1 SbF the ligand adopts a dianionic open-shell
electronic configuration, with enhanced Lewis acidity at the
metal. The reaction then evolves towards isomerization into
phenylacetaldehyde.
Experimental section
Materials and instruments
6
| J. Name., 2012, 00, 1-3
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DOI: 10.1039/C6DT02163H
PAPER
+
-
All operations were performed under anaerobic conditions 35.4, 34.6, 31.7, 31.2. MS (ESI): m/z= 809.6 [M + H] . IR:
ν
(cm
) = 3288, 2949, 2905, 2867, 1587, 1568, 1302, 1226. Anal.
Schlenk techniques. Anhydrous toluene, DMF and Calcd for C57 : C, 84.62; H, 7.98; N, 3.47. Found: C,
triethylamine were distilled over CaH under an argon 84.64; H, 7.74; N, 3.79.
atmosphere prior to use. Anhydrous acetone, dppH Under argon, NaH (293 mg, 7.3 mmol, 4.0 equiv.) was
1
under a pure argon atmosphere using a glovebox or standard
64 2 2
H N O
2
3
.
dichloromethane, acetonitrile, methanol were purchased from added to a solution of n-dodecanethiol (1.75 mL, 7.3 mmol, 4.0
Acros. 2-(3,5-Di-tert-butyl-2-methoxyphenyl)pyrrole and 2,6- equiv.) in DMF (20 mL) at 5°C. The temperature was allowed to
diphenylbenzaldehyde were prepared according to reported warm to 25°C and the mixture was stirred during 1 hour.
[
18,19]
procedures.
Acros, Alfa-Aesar, Sigma-Aldrich or TCI and were used as the reaction was heated at 110°C during 4 hours. After cooling
received. NMR spectra were recorded on a Brüker Avance 300 to rt, saturated aq. NH Cl, H O and EtOAc were added. The
H at 300 MHz, C at 75 MHz). Chemical shifts are given organic layer separated and the aqueous one was extracted
relative to solvent residual peaks. Mass spectra were recorded with EtOAc. The combined organic phase was dried over
on Brüker Esquire 3000 (ESI/Ion Trap) equipment. Na SO , filtrated and concentrated under reduced pressure.
Microanalyses were performed by the Service Central The remaining residue was purified by crystallization in a
Analyze du CNRS (Lyon, France). Infrared spectra were MeOH/CH Cl mixture afforded the ligand as dark red needles.
2
All other chemicals were purchased from dppHMe (1.46 g, 1.8 mmol, 1.0 equiv.) was then added and
4
2
1
13
(
a
2
4
d
′
2
2
1
recorded on
3
a Thermo Scientific Nicolet iS10 FT-IR Yield: 69%. H NMR (300 MHz, CDCl ): δ (ppm)= 7.60 (dd, J =
spectrometer equipped with an ATR sampling accessory. 8.3, 7.0 Hz, 1H), 7.47-7.44 (m, 4H), 7.31 (d, J = 2.4 Hz, 2H),
UV/Vis visible spectra at 298 K were recorded on a Varian Cary 7.25-7.21 (m, 4H), 7.19-7.08 (m, 6H), 6.76 (d, J = 4.4 Hz, 2H),
1
0 spectrometer. X-band EPR spectra were recorded either on 6.60 (d, J = 4.4 Hz, 2H), 1.49 (s, 18H), 1.33 (s, 18H); C NMR
3
5
an EMX plus spectrometer equipped with an Oxford Helium (75 MHz, CDCl ): δ (ppm)= 153.8, 153.0, 143.3, 141.8, 141.4,
3
cryostat. Spectra were treated using the Bruker SIMFONIA 141.2, 135.9, 135.5, 135.3, 129.8, 129.4, 129.0, 128.6, 127.8,
software. Cyclic voltammetry curves were recorded on a CH 127.0, 125.4, 123.0, 118.1, 116.6, 35.0, 34.5, 31.7, 30.4. MS
+
-1
Instruments 620 potentiostat in a standard three-electrode (ESI): m/z= 781.6 [M + H] . IR:
cell under argon atmosphere in CH Cl solutions containing 2905, 2867, 1559, 1476, 1242. Anal. Calcd for
.1M tetrabutylammonium perchlorate (TBAP) as supporting .CH OH: C, 82.72; H, 7.93; N, 3.45. Found: C, 82.42;
(0.01 M) reference electrode was H, 7.96; N, 3.30.
ν (cm ) = 3626, 3449, 2958,
2
2
0
C
55
H
60
N
2
O
2
3
electrolyte. An Ag/AgNO
3
used. All the potentials given in the text are referred to the Complex 1. Under argon, Mn(OAc)
3
.2H
L, 0.32 mmol, 5.0 equiv.) were added
glassy carbon disc electrode (5 mm diameter), polished with 1 dropwise to a stirred solution of dppH3 (50 mg, 0.064 mmol,
m diamond paste, was used as the working electrode. 1.0 equiv.) in a CH Cl /MeOH (3:1, v:v) mixture (15 mL). The
Electrochemical oxidations were performed on an EG&G PAR reaction was heated at 50°C and was completed within 2 hours
73A potentiostat, under an argon atmosphere at 298 K, using (TLC monitoring; Eluent: CH Cl /pentane; 1:1, v:v). After
2
O (34 mg, 0.13 mmol,
+
3
regular Fc /Fc redox couple used as an internal reference. A 2.0 equiv.) and Et N (45 ꢁ
ꢁ
2
2
2
2
2
a carbon foam working electrode.
cooling to r.t. the volatiles were removed under reduced
pressure. The remaining residue was purified by column
Synthesis
2 2
chromatography (CH Cl /pentane; 1:1, v:v) to give the desired
complex. Dark brown powder, yield: 74%. Dark crystals were
grown by slow diffusion of pentane in a CH Cl / MeOH
dppHMe
.437 mmoles, 0.5 equiv.) and TFA (10
mol%) were added to a stirred solution of 2-(3,5-di-tert-butyl-
-methoxyphenyl)pyrrole (500 mg, 0.876 mmoles, 1.0
2
. Under argon, 2,6-diphenylbenzaldehyde (113 mg,
[18]
2
2
-
0
ꢁL, 0.131 mmoles, 15
-
solution of the complex. MS (ESI): m/z= 832 [M - H] . IR:
ν
(cm
= 2946, 2904, 2867, 1546, 1486, 1397, 1287, 1017, 859, 695.
Anal. Calcd for C H MnN O , 3 CH OH: C, 74.98; H, 7.48; N,
1
)
2
[
19]
5
5
57
2
2
3
2 2
equiv.) in CH Cl (5 mL) at room temperature. After 24 hours
3
.02. Found: C, 74.73; H, 7.45; N, 3.09.
stirring, DDQ (99 mg, 0.436 mmoles, 0.5 equiv.) was added in
small portions. The resulting mixture was allowed to stir 2.5
more hours at room temperature before saturated aqueous
+
-
Complex 1 SbF
equiv.) was added to a solution of 1 (20 mg, 0.025 mmol, 1.0
equiv.) in CH Cl (10 mL). After 10 min stirring at r.t., the
6 6
. Under argon, AgSbF (9.9 mg, 0.03 mmol, 1.2
2
2
NaHCO
separated and the aqueous one was extracted with CH
combined organic phase was dried over Na SO , filtrated and
3
was added dropwise. The organic phase was
mixture was filtrated on Celite® and the resulting filtrate was
concentrated to a volume of about 1 mL. Addition of pentane
under vigorous stirring at 5°C formed a precipitate. Filtration
through a frit gave a dark red powder. Yield: 97%. Blue crystals
2
2
Cl . The
2
4
concentrated under reduced pressure. The remaining residue
was triturated in MeOH, filtrated through a frit and dried
+
-
of 1 SbF
6
were grown by slow diffusion of pentane in a CH
2
Cl
2
under vacuum to give the desired compound as an orange-red
1
solid. Yield: 84%. H NMR (300 MHz, CDCl
+
solution of the complex. MS (ESI): m/z= 832.5 [M - SbF ] . IR:
6
ν
cm ) = 3462, 2949, 2901, 2867, 1530, 1518, 1429, 1397, 1363,
3
):
δ
(ppm)= 7.59 (dd,
-1
(
J = 8.2, 6.7 Hz, 1H), 7.46 (d, J = 7.4 Hz, 2H), 7.37-7.27 (m, 8H),
.14 – 7.03 (m, 6H), 6.49 (s, 4H), 3.18 (s, 6H), 1.36 (s, 18H),
1
252, 1103, 1014, 960. Anal. Calcd for C55 , 2 CH Cl :
2
H
61MnN
2
O
4
2
7
1
3
C, 53.71; H, 5.14; N, 2.19. Found: C, 54.13; H, 5.27; N, 2.11.
1
1
1
3
.28 (s, 18H); C NMR (75 MHz, CDCl ): δ (ppm)= 155.8, 153.4,
45.3, 143.3, 142.8, 142.1, 141.9, 135.9, 135.1, 129.3, 129.7,
Catalytic experiments
28.6, 128.5, 127.6, 127.1, 126.5, 124.9, 124.7, 119.0, 61.0,
This journal is © The Royal Society of Chemistry 20xx
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DOI: 10.1039/C6DT02163H
PAPER
Reactions were carried using stock solutions containing 0.1 M
Dalton Trans.
Aknowledgements
-2
of styrene and 5.10 M of biphenyl (internal standard) in
CH Cl . A typical run was performed as follows: in a vial, PhIO
1 or 2 equiv) and the desired complex
2
2
+
-
This work is supported by a NSERC Discovery Grant (T. S.) from
Canada and the Labex Arcane (ANR-11-LABX-0003-01, F. T.).
The authors thank the FFCR program for travelling grants.
(
6
1 or 1 SbF (1 mol%)
were successively added to 2 mL of the stock solution. The
mixture was stirred at room temperature during 20h, filtrated
through coton and analyzed by GC. GC analyses were done on
a Shimadzu GC-17A apparatus equipped with a BPX5 capillary
column (30 m x 0.25 mm). Analytical method: Injector temp.:
References
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1
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[
31]
[32]
9 program (Revision D.01), the B3LYP functional and the
0
6
1
-31G(d) basis set on all atoms. The X-ray crystal structures of
+
and
1
2•H
2
O were used as a starting point for all geometry
2
a) K. Srinivasan, P. Michaud, J. K. Kochi, J. Am. Chem. Soc.,
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3
4
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[28]
B3LYP functional with a polarized continuum model (PCM)
[33]
for CH
Ahlrichs on all atoms.
energy electronic transitions for
2
Cl
2
(dielectric ε[ = 8.94) , and the TZVP basis set of
34]
,
The intensities of the 30 lowest-
638-41. b) A. K. Nairn, R. Bhalla, S. P. Foxon, X. Liu, L. J.
+
1
were calculated by TD-
at the B3LYP/TZVP level with a PCM for CH Cl
was used for determining atomic orbital
[35]
DFT
AOMix
2
2
.
[36]
compositions employing Mulliken Population Analysis.
Crystal structure analysis
5
6
a) A. Kochem, H. Kanso, B. Baptiste, H. Arora, C. Philouze, O.
Jarjayes, H. Vezin, D. Luneau, M. Orio, F. Thomas, Inorg.
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The collected reflections were corrected for absorption
[37]
(SADABS)
and solved by direct methods and refined with
[38]
Olex software. All non-hydrogen atoms were refined with
anisotropic thermal parameters. Hydrogen atoms were
generated in idealized positions, riding on the carrier atoms,
with isotropic thermal parameters. CCDC-1449350 and
2
016, 55, 762-774.
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,
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1
482036 contains the supplementary crystallographic data for
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Conclusions
In summary we prepared the Mn(III)-bis(phenolate)dipyrrin
complex
1. We establish that 1 undergoes two oxidative
ligand-centered redox processes, producing the persistent
+
Wasinger and T. D. P. Stack, J. Am. Chem. Soc., 2012, 134
,
2+
radical species
1
and the dication
1
. We structurally
-
7367. j) K. Asami, K. Tsukidate, S. Iwatsuki, F. Tani, S.
Karasawa, L. Chiang, T. Storr, F. Thomas, Y. Shimazaki, Inorg.
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Thomas, O. Jarjayes, C. Philouze, E. Saint-Aman, J.-L. Pierre,
Chem. Eur. J., 2006, 12, 6953-62. c) O. Rotthaus, O. Jarjayes,
+
characterized an unique Mn(III)-phenoxyl radical (1 SbF
6
) and
report the first evidence of control of the reactivity for styrene
oxidation by changing the oxidation state of a catalyst based
+
on a redox-active ligand. Both
1
and
1
indeed catalyze
styrene oxidation in the presence of PhIO, but the nature of
the main reaction product is controlled by the initial oxidation
state of the precatalyst: Styrene oxide is the main reaction
7
product when using
1, but phenylacetaldehyde is formed
+
predominantly when using
1
.
8
| J. Name., 2012, 00, 1-3
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Ple Da sae l tdo onn To rt aa nd sj ua sct t mi o an r sg ins
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DOI: 10.1039/C6DT02163H
PAPER
C. P. Del Valle, C. Philouze, F. Thomas, Chem. Commun., 15 V. Lyaskovskyyn, B. de Bruin, ACS Catal., 2012,
2
2
007, 4462-64. d) O. Rotthaus, O. Jarjayes, F. Thomas, C. 16 S. El Ghachtouli, K. Wojcik, L. Copey, F. Szydlo, E. Framery, C.
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DOI: 10.1039/C6DT02163H
PAPER
Dalton Trans.
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Ple aDs ae l dt oo nn To rt a and sj ua sc tt imo na sr gins
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PAPER
Graphical abstract:
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DOI: 10.1039/C6DT02163H
One electron-oxidation produces a structurally characterized
Mn(III) radical complex, which catalyzes the isomerization of
epoxides in addition to the epoxidation of olefins in the
presence of PhIO.
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