Structure and Reactivity of a Mononuclear Nonheme Manganese(III)-Iodosylarene Complex

Article abstract of DOI:10.1021/jacs.8b10244

Transition metal-iodosylarene complexes have been proposed to be key intermediates in the catalytic cycles of metal catalysts with iodosylarene. We report the first X-ray crystal structure and spectroscopic characterization of a mononuclear nonheme manganese(III)-iodosylarene complex with a tetradentate macrocyclic ligand, [Mn^III(TBDAP)(OIPh)(OH)]²⁺ (2). The manganese(III)-iodosylarene complex is capable of conducting various oxidation reactions with organic substrates, such as C-H bond activation, sulfoxidation and epoxidation. Kinetic studies including isotope labeling experiments and Hammett correlation demonstrate the electrophilic character on the Mn-iodosylarene adduct. This novel intermediate would be prominently valuable for expanding the chemistry of transition metal catalysts.

Full text of DOI:10.1021/jacs.8b10244

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Communication
Structure and Reactivity of a Mononuclear
Nonheme Manganese(III)-Iodosylarene Complex
Donghyun Jeong, Takehiro Ohta, and Jaeheung Cho
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b10244 • Publication Date (Web): 08 Nov 2018
Downloaded from http://pubs.acs.org on November 8, 2018
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Structure and Reactivity of a Mononuclear Nonheme Manganese(III)-
Iodosylarene Complex
Donghyun Jeong,† Takehiro Ohta,‡ Jaeheung Cho*,†
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† Department of Emerging Materials Science, DGIST, Daegu 42988, Korea
‡
Picobiology Institute, Graduate School of Life Science, University of Hyogo, RSC-UH LP Center, Hyogo 679-5148, Japan
Supporting Information Placeholder
through binding to metal center followed by O-I bond cleavage.6
ABSTRACT:
Transition metal-iodosylarene complexes have been
However, it has been continuing controversy whether metal-
iodosylarene adducts, instead of the corresponding high-valent
metal-oxo species, are able to oxidize organic substrates in the cata-
lytic systems (i.e., multiple-oxidant mechanism) (Scheme 1).7 Dur-
ing past two decades, various spectroscopic and kinetic evidences
have supported the involvement of intervening metal-iodosylarene
species in oxidative catalytic reactions by metal catalysts with iodo-
sylarene over single-oxidant mechanism (e.g., sole metal(IV/V)-
oxo species).8-10 In the 1990s, for examples, Valentine and co-
workers revealed that epoxidation of olefin was significantly en-
hanced by using PhIO and redox-inactive metals such as alumi-
num(III) and zinc(II) which are inaccessible to corresponding
high-valent metal-oxo species.8 In the 2000s, Nam et al. suggested
multiple-oxidant mechanism in the catalytic olefin epoxidation by
an iron porphyrin complex based on the product analysis where the
ratio of stereoisomers is dependent on terminal-oxidants or counter
anions.9 Recently, Lei and co-workers reported spectroscopic evi-
dence for a transient manganese(III)-iodosylarene porphyrin spe-
cies as a precursor of high-valent manganese(V)-oxo species.10
proposed to be key intermediates in the catalytic cycles of metal
catalysts with iodosylarene. We report the first X-ray crystal struc-
ture and spectroscopic characterization of a mononuclear nonheme
manganese(III)-iodosylarene complex with a tetradentate macro-
cyclic ligand, [MnIII(TBDAP)(OIPh)(OH)]2+ ( ). The manga-
2
nese(III)-iodosylarene complex is capable of conducting various
oxidation reactions with organic substrates, such as C-H bond acti-
vation, sulfoxidation and epoxidation. Kinetic studies including
isotope labeling experiments and Hammett correlation demon-
strate the electrophilic character on the Mn-iodosylarene adduct.
This novel intermediate would be prominently valuable for expand-
ing the chemistry of transition metal catalysts.
High-valent metal-oxo species have been widely considered as a
key intermediate in various oxidative reactions of biological sys-
tems.1 For examples, high-valent heme and nonheme iron-oxo
species in cytochromes P450 and nonheme iron enzymes, respec-
tively, are responsible for the metabolic conversion of organic sub-
strates.2-3 Nonheme manganese-oxo adducts have also received
much interest from biologists and bio-inorganic chemists because
they have been postulated as putative intermediates in the oxygen
evolving cluster (OEC) of photosystem II where water splitting
and dioxygen molecule formation occur as well as in the oxidative
catalytic reaction by manganese catalysts.4-5
Scheme 2. Overall Synthetic Procedures for the Mn(III)-Iodosylarene
Complex from a Starting Material with PhIO.
N
N
N
2+
2+
I
PhIO
PhIO
OTf
OTf
OH
OH
O
N
N
N
MnII
MnIV
MnIII
In synthetic chemistry, iodosylarenes have been used as artifi-
cial oxidants to afford high-valent metal-oxo complexes because it is
capable of simple oxygen atom transfer reaction to a metal complex
N
N
N
OH
N
N
N
[MnII(TBDAP)(OTf)2]
[MnIV(TBDAP)(OH)2]2+ (1)
[MnIII(TBDAP)(OIPh)(OH)]2+ (2)
Scheme 1. Possible Mechanisms of Oxidation Reactions by Metal
Catalysts using Iodosylbenzene (PhIO) as an Oxidant.
Very recently, a few of nonheme metal-iodosylarene complexes
have been synthesized and characterized using various spectroscop-
ic and crystallographic methods.11-12 Their reactivity studies
demonstrated that the metal-iodosylarene species have oxidizing
power towards organic substrates. McKenzie's, Fujii's and Ander-
son's groups reported the first crystal structure of nonheme
iron(III), manganese(IV) and cobalt(II)-iodosylarene complexes,
respectively, which are responsible for oxidative reactions.11 Nam
and co-workers reported the activation of strong C-H bond on
hydrocarbons by a nonheme iron(III)-iodosylarene complex.12
Product Substrate
Multiple-Oxidant Mechanism
OIPh
LMn+
O
PhIO
-PhI
LMn+
LM(n+2)+
Substrate
Product
Single-Oxidant Mechanism
1
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Figure 2. ORTEP diagram of 2
with thermal ellipsoids drawn at the 30%
probability level. Hydrogen atoms are omitted for clarity except for a
hydrogen atom on the hydroxo ligand (gray, C; cyan, H; blue, N; red,
O; green, I; violet, Mn).
to-charge ratio (m/z) of 322.1 with a mass and isotope pattern
16
corresponding to [Mn(TBDAP)(OIPh)(OH)]2+ ( - O) (calcu-
2
lated m/z of 322.1) (Figure 1b). When was formed with isotopi-
2
mass peak corresponding to
cally labeled PhI18O,
a
18
[Mn(TBDAP)(18OIPh)(18OH)]2+ ( - O) appeared at m/z of
324.1 (calculated m/z of 324.1). The resonance Raman spectrum
2
Figure 1. (a) UV-vis spectral changes observed in the reaction of
[MnII(TBDAP)(OTf)2] (1.0 mM, black) with PhIO (3.0 mM) in
2
of
was obtained using 355 nm laser excitation in
2
CH3CN/CF3CH2OH (v/v = 3:1) at 20 °C.
the formation of (green). The inset exhibits the resonance Raman
spectra of
-16O (red) and -18O (blue), which were measured in the
excitation at 355 nm in CH3CN/CF3CH2OH. (b) ESI-MS spectrum
of The peak at m/z 322.1 corresponds to
-16O. Insets show
observed isotope distribution patterns for
-16O (red) and -18O (blue).
2
(red) is generated via
CH3CN/CF3CH2OH (v/v = 3:1) at –20 °C (Figure 1a, inset). -
16O shows an isotope sensitive band at 623 cm-1, which shifts to 598
cm in - O. The obtained value of 623 cm is comparable to the
observed Mn-O-I stretching band in [MnIV(salen)(OIPh)2Cl2]
(vMn-O-I = 608 cm-1).11b
1
2
2
-1
18
-1
2
2
.
2
2
2
Brown crystals suitable for X-ray diffraction were obtained as
2
triflate salt by diffusion of diethylether into a solution of in
However, to the best our knowledge, there is no evidence for exist-
ence of nonheme manganese(III)-iodosylarene species despite of
long-standing chemical research of manganese catalysts. Herein, we
report the first generation of a nonheme manganese(III)-
CH3CN/CF3CH2OH (v/v = 3:1) at 0 °C (SI, Table S1 and S2 for
2
2
crystallographic data of ). Ortep structure of reveals the mono-
nuclear end-on manganese-iodosylarene complex with the cis-
oriented hydroxide ion in distorted octahedral geometry (Figure 2).
Noteworthy is that this crystal structure is the first example of man-
ganese(III)-iodosylarene species. The Mn-OIPh bond length is
1.904(4) Å, which is longer than the Mn-OH distance (1.832(4)
iodosylarene complex, [MnIII(TBDAP)(OIPh)(OH)]2+ ( ;
2
TBDAP = N,N-di-tert-butyl-2,11-diaza[3.3](2,6)-pyridinophane),
together with the single crystal structure and spectroscopic analyses
2
(Scheme 2). The reactivity of was investigated in electrophilic
2
Å). The O-I bond distance in (1.929(5) Å) is comparable to that
hydrogen atom abstraction (HAA) and oxygen atom transfer
(OAT) reactions.
of [FeIII(tpena)(OIPh)]2+ (1.920(3) Å).11a Taken together, the
2
structural and spectroscopic analyses indicate clearly that is a
2
Complex
is prepared by the reaction of
manganese(III)-iodosylarene complex.
2
[MnII(TBDAP)(OTf)2] with an excess amount of iodosylbenzene
(PhIO) in CH3CN/CF3CH2OH (v/v = 3:1) at 20 °C via the for-
The oxidative reactivity of was investigated in the hydrocar-
bon activation of substrates with the C-H bond dissociation ener-
gies (BDEs) in the range of 75.5 – 78 kcal mol-1, such as 1,4-
cyclohexadiene (CHD, 78 kcal mol-1), 9,10-dihydroanthracene
(DHA, 77 kcal mol-1), and xanthene (75.5 kcal mol-1).15 Upon addi-
IV
2+
mation of [Mn (TBDAP)(OH)2] ( ) intermediate (Figure 1a).
1
Recently, we have reported the formation of , which was generat-
1
ed by adding equiv of PhIO into solution of
1
[Mn (TBDAP)(OTf)2] at low temperature. Indeed, is accessi-
a
II
13
2
2
tion of DHA to a solution of in CH3CN/CF3CH2OH (v/v = 3:1)
at 20 °C, the characteristic absorption band of at 710 nm decayed
1
ble when reacts with PhIO at 20 °C (Figure S1). In a typical ex-
2
2
periment for the generation of , 3 equiv of PhIO is added into a
obeying first-order kinetics (Figure 3a). Product analysis obtained
from the reaction solution revealed that anthracene (84 ± 5%) was
solution of [MnII(TBDAP)(OTf)2] at 20 °C. The metastable
2
brown complex exhibits the weak UV-vis absorption band at 710
produced, and [MnIII(TBDAP)(OH)(X)]+ (X = OTf– and
nm (ꢀ = 100 cm–1 M–1) and shoulder at 430 nm (ꢀ = 480 cm–1 M–1)
in CH3CN/CF3CH2OH (v/v = 3:1) at 20 °C (t1/2 ≈ 2 h).
–
CF3CH2O ) was found to be a decomposed product of in the
2
oxidation reaction of DHA (Figure S4). Pseudo-first-order rate
constants increased proportionally with increasing the concentra-
tion of DHA (Figure 3b). Thus, the second-order rate constant for
2
The X-band EPR spectrum of was silent, indicating integer
spin state of Mn center (Figure S2). Magnetic moment of was
2
determined to be 5.1 µB from Evans' NMR method,14 which is in-
-1 -1
2
the reaction of with DHA was determined to be 2.7(1) M s . A
kinetic isotope effect (KIE) value of 4.0 was obtained from the
2
dicative of S = 2 spin state for . Electrospray ionization mass spec-
trometry (ESI-MS) spectrum of reveals a positive signal at mass-
2
2
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Figure 4. Reactions of 2
with thioanisole in CH3CN/CF3CH2OH (v/v
= 3:1). (a) Plot of second-order rate constants against 1/T to deter-
Figure 3. (a) UV-vis spectral changes of
2
(1 mM, red) upon addition
of DHA (25 mM) in CH3CN/CF3CH2OH at 20 °C. Inset shows the
time course of the absorption band at 710 nm. (b) Plots of pseudo-
first-order rate constants (kobs) against the concentration of DHA (red)
and DHA-d4 (purple) to determine second-order rate constants (k2).
+
mine activation parameters. (b) Hammett plot of lnk2 against sp of
thioanisole derivatives in the reaction of (1 mM) with para-X-Ph-
2
SMe (X = Me, F, H, Cl, Br) in CH3CN/CF3CH2OH at 0 °C.
substituents gave a
value of -7.4(2). The negative value indi-
r r
comparison of reaction rates in the oxidation of DHA and deuter-
2
cates the electrophilic reactivity of in OAT reaction.
2
2
ated DHA (DHA-d4) by (Figure 3b) indicating that HAA by is
a rate-determining step. Further, second-order rate constants for
the oxidation reaction of other substrates were also obtained (Ta-
ble S4, and Figures S5 and S6).
2
Lastly, the reaction of with olefin such as trans- and cis-
stilbene afforded corresponding olefin oxides accompanying high
2
stereoselectivity. Kinetics for the olefin oxidation by were fol-
lowed by spectroscopically (Figure S10). Second-order rate con-
stants for trans- and cis-stilbene oxidation reaction were deter-
mined to be 2.4(1) × 10–1 M–1 s–1 and 1.9(1) × 10–2 M–1 s–1, respec-
tively, from linear plotting of pseudo-first order rate constants vs.
the concentrations of stilbene (Figure S11). Product analysis of the
OAT reaction was also performed in the oxidation of thioan-
2
isole and stilbene derivatives by in CH3CN/CF3CH2OH (v/v =
3:1) at 20 °C. Upon addition of excess amount of thioanisole to a
2
solution of , the absorption band at 710 nm disappeared with a
first-order decay profile (Figure S6). Second-order rate constant
2
reaction solution of the trans- and cis- stilbene oxidation by re-
2
for the oxidation of thioanisole by was determined to be 1.1(1)
M–1 s–1 by plotting of pseudo-first-order reaction rates against the
concentrations of thioanisole (Figure S7). Product analysis, ob-
vealed the formation of trans- and cis-stilbene oxide as a major
product with 42(3)% and 37(4)% yield, respectively, demonstrat-
2
ing that is highly stereospecific in the epoxidation reaction. The
origination of oxygen atom in the stilbene oxide was found to be
2
tained from the reaction solution of with thioanisole, revealed
that methyl-phenyl-sulfoxide (63 ± 5%) as a major product was
18
produced. Further, when the reaction was performed with - O,
derived from the manganese-iodosylarene species when the reac-
2
2
18
tion was performed by - O (Figure S12). Finally, it is found that
2
the oxygen atom in the methyl-phenyl-sulfoxide was found to be
originated from the MnIII-OIPh species (Figure S8). In addition,
[MnIII(TBDAP)(OH)(X)]+ (X = OTf– and CF3CH2O–) were ob-
2
served in the reaction solution as decomposed products of (Fig-
ure S9).
was converted to Mn(III) species after the epoxidation reaction
(Figure S13).
Based on the kinetic studies and product analyses, plausible
2
reaction mechanisms for the oxidative reaction by in HAA and
OAT reactions are summarized in Scheme 3. In the HAA reaction,
Temperature-dependence of the reaction rates in the oxidation
2
substrate affording and PhI. Thus, we examined in the C-H
has performed rate-determining C-H bond activation of the
1
2
of thioanisole by was observed in the range of 263 – 293 K. A
linear Eyring plot gives activation parameters for ΔH‡ of 11.9(6)
kcal mol–1 and ΔS‡ of –17.6(14) cal mol–1 K–1 (Figure 4a). The
observed negative value of entropy and second-order kinetics sug-
1
1
bond activation reaction (Figure S14). Indeed, it is revealed that
is capable of the C-H bond activation having more oxidizing power
2
than . This result is in good agreement with the hypothesis that
the C-H bond activation by
2
gest that the oxidation of thioanisole by occurs through a bimo-
lecular mechanism. The reaction of with para-substituted thioan-
2
is the rate-determining step.
2
1
Therefore, oxidizes an additional substrate again and decompose
2
isole derivatives, para-X-Ph-SMe (X = Me, F, H, Cl, Br), was exam-
2
III
to the Mn species. In the OAT reaction, directly transfer the
ined to assess the nature of Mn-iodosylarene moiety of in the
thioanisole oxidation reaction (Figure 4b). The Hammett plot of
oxygen atom from the Mn-OIPh moiety to the substrate via two-
electron pathway resulting MnIII species.
+
the pseudo-first-order rate constants against sp of para-
3
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Scheme 3. Proposed Mechanisms for the HAA and OAT reactions of
various substrates by 2.
for Accelerating Brain Circulation to T.O.” and Grant-in-Aid for
Scientific Research (No. 15H00960 to T.O.).
1
2
3
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2
The reaction rate of with DHA is similar to those of highly
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2
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possesses
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ASSOCIATED CONTENT
Supporting Information.
Experimental details, Tables S1–S4, and Figures S1–S16. This
material is available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*jaeheung@dgist.ac.kr
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENT
The research was supported by NRF (2017R1A2B4005441 and
2018R1A5A1025511 to J.C.) and the Ministry of Science, ICT and
Future Planning (CGRC 2016M3D3A01913243 and DGIST
R&D Program 19-BD-0403 to J.C.) of Korea, and the Ministry of
Education, Culture, Sports, Science and Technology of Japan
through the “Strategic Young Researcher Overseas Visits Program
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