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Rhodium-Mediated Formation of Peroxides from Dioxygen Isolation of Hydroperoxo Silylperoxo and Methylperoxo Intermediates.

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Angewandte
Chemie
Peroxo Complexes
DOI: 10.1002/anie.200501615
Rhodium-Mediated Formation of Peroxides from
Dioxygen: Isolation of Hydroperoxo, Silylperoxo,
and Methylperoxo Intermediates**
Marcel Ahijado, Thomas Braun,* Daniel Noveski,
Nikolaus Kocher, Beate Neumann, Dietmar Stalke, and
Hans-Georg Stammler
Peroxo and hydroperoxo transition-metal complexes have
been suggested to play a key role as intermediates in several
oxygenation processes with molecular oxygen, including
reactions mediated by cytochrome P450, the catalytic oxidation of olefins, and the generation of peroxides.[1, 2] A hydroperoxo ligand can also be found in oxyhemerythrin which is
produced when dioxygen is bound at the nonheme oxygen
carrier hemerythrin.[3] The oxygen atoms of h2-bound peroxo
ligands at electron-rich transition metals are usually nucleophilic.[4] This is reflected in the formation of hydrogen
peroxide or trityl peroxide from h2-peroxo complexes and
the corresponding electrophilic sources (trityl = triphenylmethyl).[4–6] Hydroperoxo and alkylperoxo complexes are
thought to be intermediates in these reactions, but there is
extremely little precedent on their identification.[4, 7] The
conversion of coordinated oxygen into an OOR ligand (R =
alkyl, H) can be considered to be one of the key steps in these
transformations, but even model reactions for the formation
of oxygen-derived hydroperoxo and alkylperoxo species are
very sparse.[2a, 4, 7–9] Stahl et al. showed that protonation of
palladium h2-peroxo species, bearing N-heterocyclic carbene
ligands, with acetic acid leads to h1-hydroperoxo compounds,
which can be further protonated to give hydrogen peroxide.[7]
[*] M. Ahijado, Dr. T. Braun, D. Noveski, B. Neumann,
Dr. H.-G. Stammler
Fakult*t f,r Chemie, Universit*t Bielefeld
Postfach 100131, 33501 Bielefeld (Germany)
Fax: (+ 49) 521-106-6026
E-mail: thomas.braun@uni-bielefeld.de
Dr. N. Kocher, Prof. Dr. D. Stalke
Institut f,r Anorganische Chemie der Universit*t G=ttingen
Tammannstrasse 4, 37077 G=ttingen (Germany)
[**] This research was supported by the Deutsche Forschungsgemeinschaft. We also thank Prof. P. Jutzi for his support.
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
Angew. Chem. Int. Ed. 2005, 44, 6947 –6951
The presence of the h1-hydroperoxo complex and of its 18Olabeled isotopologue has been confirmed by comparison of
the mass spectrometric data with simulated spectra. Otsuka
et al. reported that the reaction of [Pt(O2)(PR3)2] (R = Ph,
Cy) with BrCPh3 leads to the tritylperoxo complexes [PtBr(OOCPh3)(PR3)2].[4] These complexes can be converted into
Ph3COOCPh3 and are presumably stabilized kinetically by
the steric bulk of the trityl group. Moro-oka et al. found that a
rhodium h2-peroxo complex can be protonated with pyrazole.[9] The hydroperoxo species obtained is stabilized by a
hydrogen bond between a pyrazole ligand and the b-oxygen in
the hydroperoxo ligand. No further reactivity of this compound has been reported.
In this communication we report on the sequential
conversion of molecular oxygen into hydrogen peroxide as
well as into silyl and methyl peroxides via h1-hydroperoxo, h1silylperoxo, and h1-methylperoxo complexes. Not only the
isolation of the intermediate species bearing an OOSiMe3 or
OOMe ligand is unprecedented, but also h1-silylperoxo and
h1-methylperoxo complexes have for the first time been
unambiguously characterized by IR spectroscopy and X-ray
crystallography. The stabilizing effect of a tetrafluoropyridyl
ligand bound at rhodium[10] presumably allows the isolation of
the intermediates.
Exposure of a hexane solution of the tetrafluoropyridyl
complex 1[10] to air or oxygen slowly leads to the generation of
the dioxygen compound 2 a within hours (Scheme 1). Similarly, treatment of 1 with 18O2 gives the peroxo complex trans[Rh(18O2)(4-C5F4N)(CNtBu)(PEt3)2] (2 b). Note that Selke
et al. reported the formation of the complex trans-[Rh(SC6F5)(O2)(CO)(PPh3)2], which is unstable at room temperature, using singlet oxygen.[11] In contrast, the formation of 2 a
and 2 b is spin-forbidden and requires a triplet–singlet surface
crossing on the reaction coordinate.[12] The 19F NMR spectrum of 2 a displays four signals for the tetrafluoropyridyl
ligand indicating hindered rotation (Table 1).[10] The rhodium–phosphorus coupling constant of 87 Hz in the 31P NMR
spectrum suggests the formation of a rhodium(iii) complex. In
the IR spectrum of 2 a an absorption band at 852 cm 1 can be
detected. The band shifts to 805 cm 1 for the 18O-labeled
isotopologue 2 b and can be assigned unequivocally to the O–
O stretching vibration of the h2-peroxo ligand.[9, 13] The
difference Dñ = 47 cm 1 is fully consistent with a simple
model for a diatomic harmonic oscillator.[14]
Figure 1 shows the molecular structure of 2 a determined
by X-ray crystallography.[15] The molecule exhibits a distorted
octahedral structure, if the oxygen is treated as a bidentate
ligand. Alternatively if the dioxygen is treated as occupying a
single coordination site, the structure is approximately
trigonal-bipyramidal with two phosphine ligands occupying
the axial sites. The O O distance of 1.452(3) ; is similar to
the corresponding bond length found in cis-[Rh(CF3)(O2)(CNXy)2(PPh3)] (1.438(3) ;; Xy = 2,6-Me2C6H3) and is also
in the same range as these observed in other rhodium h2peroxo complexes.[16]Treatment of complex 2 a with a solution
of HCl in Et2O affords the dichloro compound 4 and H2O2
(Scheme 1). Low-temperature NMR experiments at 213 K
reveal the formation of 3 as the initial product. A broad signal
in the 1H NMR spectrum at d = 7.35 ppm can be attributed to
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Scheme 1. The synthesis and reactivity of rhodium peroxo compounds. 2 b, 5 b, and 6 b are 18O isotopologues of 2 a, 5 a, and 6 a, respectively.
Table 1: Selected NMR spectroscopic data.[a]
2 a: 19F NMR (C6D6): d = 98.1 (m, 1 F), 98.6 (m, 1 F), 107.6 (m, 1 F),
117.3 ppm (m, 1 F); 31P NMR (C6D6): d = 24.6 ppm (d, 1JP,Rh = 87 Hz).
3:[b] 1H NMR ([D8]toluene): d = 7.35 ppm (br. s, OOH); 19F NMR
([D8]toluene): d = 96.1 (m, 1 F), 97.8 (m, 1 F), 115.3 (m, 1 F),
120.4 ppm (m, 1 F); 31P NMR ([D8]toluene): d = 17.8 ppm (d,
1
JP,Rh = 87 Hz).
4: 19F NMR ([D8]toluene): d = 95.3 (m, 1 F), 97.6 (m, 1 F), 110.3 (m,
1 F), 112.3 ppm (m, 1 F); 31P NMR ([D8]toluene): d = 15.3 ppm (dd,
1
JP,Rh = 80, 4JP,F = 4 Hz).
5 a: 19F NMR ([D8]toluene): d = 97.8 (m, 1 F), 99.3 (m, 1 F), 114.2
(m, 1 F), 118.1 ppm (m, 1 F); 31P NMR ([D8]toluene): d = 18.7 ppm (d,
1
JP,Rh = 87 Hz); 29Si NMR (119.2 MHz, [D8]toluene): d = 26.5 ppm (s).
6 a: 1H NMR ([D8]toluene): d = 3.64 ppm (s, 3 H, OOCH3); 19F NMR
([D8]toluene): d = 77.5 (s, 3 F, CF3), 95.9 (m, 1 F, CF), 97.9 (m, 1 F,
CF), 115.2 (m, 1 F, CF), 120.0 ppm (m, 1 F, CF); 31P NMR ([D8]toluene): d = 20.4 ppm (dd, 1JP,Rh = 86, 4JP,F = 4 Hz).
7: 1H NMR ([D8]THF): d = 3.69 ppm (s, 3 H, OOCH3); 19F NMR
([D8]THF): d = 75.7 (s, 3 F, CF3), 94.7 (m, 1 F, CF), 96.0 (m, 1 F, CF),
110.1 (m, 1 F, CF), 116.0 ppm (m, 1 F, CF); 31P NMR ([D8]THF):
d = 12.8 ppm (d, 1JP,Rh = 85 Hz).
[a] Recorded at 300 K; Measurement frequencies: 1H NMR 500 MHz,
F NMR 470.4 MHz, 31P NMR 202.4 MHz. [b] Recorded at 213 K.
19
the hydroperoxo ligand. When 2 a is treated with DCl instead
of HCl the resonance is not present. At 273 K complex 3
reacts with more HCl to give H2O2 and 4. However, even
when no further HCl is present, the slow generation of 2 a and
4 is observed. This indicates that the formation of 3 from 2 a
and HCl is reversible. The latter can react with more 3 to yield
4 and H2O2.
Compound 3 is unstable above 273 K, even in the solid
state. However, crystals of 3 suitable for X-ray crystallog-
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Figure 1. Molecular structure of 2 a in the crystal (ORTEP plot,
ellipsoids at the 50 % probability level). Selected distances [I] and
angles [8]: Rh1–O1 2.0332(16), Rh1–O2 2.0147(16), O1–O2 1.452(3);
O1-Rh1-O2 42.05(7), C13-Rh1-O2 144.08(8), C18-Rh1-O2 110.63(8).
raphy were obtained from a THF/hexane solution at 193 K.[15]
The molecular structure depicted in Figure 2 reveals that the
h1-bound hydroperoxo ligand is located in the trans position
to the isocyanide ligand. Intermolecular hydrogen bonding of
the hydroperoxo ligands also gives strong evidence for the
presence of the OOH group. These interactions result in the
formation of dimers with an intermolecular oxygen–oxygen
separation of 2.680 ; (Figure S1, Supporting Information).
The intramolecular oxygen–oxygen distance of 1.488(3) ; is
greater than that found in complex 2 a but close to the value
found for H2O2 (1.461(3) ;).[17] So far, only very few
transition-metal complexes with an h1-OOH ligand have
been structurally characterized, for example, the rhodium
compounds [(h5-C5Me5)Ir(m-pz)3Rh(OOH)(dppe)][BF4] and
[TpiPrRh(OOH)(pz)(pzH)] (pzH = pyrazole, dppe = 1,2-bis(diphenylphosphanyl)ethane, TpiPr = hydrotris(3,5-diisopropylpyrazolyl)borato).[9, 18]
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Angewandte
Chemie
in 6 a seems to be covered by a very strong broad band, which
can be attributed to the triflate ligand at 1025 cm 1.
The proposed structure of 6 a is further supported by its
reactivity. Thus 6 a reacts smoothly with pyridine to give the
cationic methylperoxo complex 7. The structure of 7 was
determined by X-ray crystallography.[15] A view of the
geometry of the cation is depicted in Figure 4. As was found
Figure 2. Molecular structure of 3 in the crystal (ORTEP plot, ellipsoids
at the 50 % probability level). Selected distances [I] and angles [8]:
Rh1–O1 2.025(2), O1–O2 1.488(3); Rh1-O1-O2 110.31(17).
The reactions of 2 a and 2 b with Me3SiCl at 213 K
furnished the silylperoxo complexes 5 a and 5 b, respectively
(Scheme 1). After warming up to 273 K the slow generation
of 4 and bis(trimethylsilyl) peroxide was observed. The latter
was identified by comparison of the NMR data with those of
an authentic sample. Compound 5 a was characterized by
NMR and IR (Table 1). Convincing evidence for the presence
of a OOSiMe3 unit is given by an absorption band at 901 cm 1
(Figure 3).[19] The signal shifts to 884 cm 1 for the isotopo-
Figure 3. Part of the IR spectra of 5 a (c) and 5 b (a).
logue 5 b. For the configuration at rhodium in 5 a and 5 b, we
assign a trans arrangement of the isocyanide and the
silylperoxo ligand, as it was found for 3. To our knowledge,
complexes 5 a and 5 b are the first transition-metal silylperoxo
compounds that have been characterized.[20]
Treatment of a toluene solution of 2 a and 2 b with MeOTf
yields the methylperoxo compounds 6 a and 6 b, respectively.
A weak absorption band at 1004 cm 1 in the IR spectrum of
6 b can be assigned tentatively to the 18O18OMe unit. The high
frequency might be attributed to a mixing of the O–O stretch
and a bending vibration. The corresponding absorption band
Angew. Chem. Int. Ed. 2005, 44, 6947 –6951
Figure 4. Structure of the cation in 7 in the crystal (ORTEP plot,
ellipsoids at the 50 % probability level). Selected distances [I] and
angles [8]: Rh1–O1 2.0196(14), O1–O2 1.479(2), O2–C18 1.412(3);
Rh1-O1-O2 111.55(10), O1-O2-C18 104.32(16).
for the hydroperoxo group in 3, the methylperoxo ligand is
located in the trans position to the isocyanide. We assume a
comparable configuration at rhodium for 6 a. The oxygen–
oxygen distance of 1.479(2) ; is similar to the O O bond
length in 3. We note that Moro-oka et al. recently reported
the crystal structure of a palladium complex with a
{PdOOtBu} unit.[18e] The structural data of two platinum
compounds with OOiPr and OOtBu ligands were published
earlier.[21] Although there are indications for the existence of
transition-metal methylperoxo complexes mainly based on
UV and NMR data, to our knowledge in none of these
compounds has the OOMe moiety been identified by IR data
or X-ray crystallography.[22]
Complex 6 a can also act as a source for organic peroxides.
Thus, treatment of a solution of the triflato compound 6 with
an excess HCl leads to complex 4 and the peroxide MeOOH,
which was identified by comparison of its 1H and 13C NMR
data with those of an authentic sample. The conversion is
quantitative according to the NMR data. We assume that the
reaction proceeds via the triflato complex trans-[Rh(Cl)(OTf)(4-C5F4N)(CNtBu)(PEt3)2], which is readily converted
into the dichloro compound 4.
In conclusion, a h1-hydroperoxo complex and for the first
time h1-silylperoxo and h1-methylperoxo species have been
characterized unambiguously by IR spectroscopy or X-ray
crystallography. The compounds are generated quantitatively
according to the NMR data and have been isolated as
intermediates in the rhodium-mediated formation of peroxides from molecular oxygen. The selective synthesis of 3, 5 a,
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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6949
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and 6 a discloses a route for the controlled preparation of
alkyl hydroperoxides and possibly dialkyl peroxides or
alkylsilyl peroxides. We believe that the stabilizing effect of
the tetrafluoropyridyl ligand with its p-acceptor properties
might be the main reason for the stability of the rhodium
complexes bearing an h1-bound peroxo unit.[10] This stability
also makes it possible to control the reactivity of the peroxo
species and accounts for the selectivity of the reactions. It is
intriguing that despite the presence of the phosphines and the
anionic carbon ligand the reactions proceed smoothly.
Neither the phosphines nor the metal-bound tetrafluoropyridyl ligand are oxygenated.
Received: May 11, 2005
Revised: July 5, 2005
Published online: October 6, 2005
.
Keywords: fluorinated ligands · oxygenation · peroxides ·
peroxo complexes · rhodium
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[15] Data for the X-ray structure analyses: 2 a: C22H39F4N2O2P2Rh,
M = 604.40, crystal dimensions 0.24 M 0.20 M 0.09 mm3 ; monoclinic; C2/c; a = 19.080(1), b = 10.283(1), c = 28.402(2) ;, b =
99.86(1) 8, Z = 8, V = 5490.2(3) ;3, 1calcd = 1.462 g cm 3 ; 2qmax =
558; MoKa radiation (l = 0.71073 ;), T = 100(2) K, 51638 reflections collected, 6294 were unique (Rint. = 0.0448); Nonius
KappaCCD diffractometer; multiscan absorption correction
(min./max. transmission 0.8337/0.9326), m = 0.787 mm 1. The
structure was solved by direct methods and refined with full
matrix least square methods on F 2 (SHELX-97).[23] Final R1, wR2
values on all data: 0.0564, 0.0680; R1, wR2 values for 4675
reflections with Io > 2s(Io): 0.0305, 0.0590; residual electron
density + 0.953/ 0.536 e ; 3 ; disorder of one triethylphosphane
ligand on two positions (89:11). 3·3 THF: C34H64ClF4N2O5P2Rh,
M = 857.17, crystal dimensions 0.40 M 0.20 M 0.05 mm3 ; monoclinic; P21/c; a = 11.7262(8), b = 15.3427(11), c = 22.9453(17) ;,
b = 101.6470(10) 8, Z = 4, V = 4043.1(5) ;3, 1calcd = 1.408 g cm 3 ;
2qmax = 52.088; MoKa radiation (l = 0.71073 ;), T = 100(2) K,
30127 reflections collected, 8265 were unique (Rint. = 0.0420);
Brukder Smart-Apex diffractometer equipped with a lowtemperature device;[24] empirical absorption correction with
SADABS 2.05 (min./max. transmission 0.7466/0.9800),[25] m =
0.626 mm 1. The structure was solved by direct methods and
refined with full matrix least square methods on F 2.[23] Hydrogen
atoms were placed at calculated positions and refined using a
riding model. Final R1, wR2 values on all data: 0.0642, 0.1191; R1,
wR2 values for 7278 reflections with Io > 2s(Io): 0.0554, 0.1155;
7:
residual
electron
density
+ 1.694/ 1.182 e ; 3.
C29H47F7N3O5P2RhS, M = 847.61, crystal dimensions 0.23 M
0.17 M 0.06 mm3 ; monoclinic; P21/n; a = 11.28100(10), b =
19.9970(2), c = 16.1900(2) ;, b = 94.3620(8) 8, Z = 4, V =
3641.66(7) ;3, 1calcd = 1.546 g cm 3 ; 2qmax = 558; MoKa radiation
(l = 0.71073 ;), T = 100(2) K, 66078 reflections collected, 8333
were unique (Rint. = 0.059); Nonius KappaCCD diffractometer;
multiscan absorption correction (min./max. transmission 0.8573/
0.9597), m = 0.691 mm 1. The structure was solved by direct
methods and refined with full matrix least square methods on F 2
(SHELX-97).[23] Final R1, wR2 values on all data: 0.0435, 0.0747;
R1, wR2 values for 6844 reflections with Io > 2s(Io): 0.0310,
0.0696; residual electron density + 0.980/ 0.582 e ; 3. CCDC265303, -271512, and -265304 contain the supplementary crystallographic data for this paper. These data can be obtained free
of charge from the Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
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6951
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peroxide, isolation, silylperoxo, methylperoxo, formation, intermediate, rhodium, dioxygen, hydroperoxy, mediated
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