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Triphenylantimony(V) o-amidophenolates with unsymmetrical N-aryl group for a reversible dioxygen binding.

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Full Paper
Received: 30 April 2010
Revised: 24 August 2010
Accepted: 8 September 2010
Published online in Wiley Online Library: 8 November 2010
(wileyonlinelibrary.com) DOI 10.1002/aoc.1738
Triphenylantimony(V) o-amidophenolates
with unsymmetrical N-aryl group
for a reversible dioxygen binding
Andrey I. Poddel’skya∗ , Yury A. Kurskiia , Alexandr V. Piskunova ,
Nikolay V. Somovb , Vladimir K. Cherkasova and Gleb A. Abakumova
New triphenylantimony(V) o-amidophenolates (AP-Me,Et)SbPh3 (1) and (AP-Me,iPr)SbPh3 (2) with unsymmetrically substituted
N-aryl groups and (AP-Et,Et)SbPh3 (3) with symmetrical N-aryl group {AP-R1 ,R2 is 4,6-di-tert-butyl-N-[2-alkyl(R1 ),6-alkyl(R2 )phenyl]-o-amidophenolate dianion} were synthesized and characterized in detail. Complexes were examined for dioxygen
activity. The unsymmetrical complexes 1 and 2 were found to form different geometrical isomers (A and B) of spiroendoperoxides
[L-R1 ,R2 (O2 )]SbPh3 (4 and 5, respectively) with different dispositions of peroxide group and N-aryl fragment (methyl and peroxide
group are on the same side of the molecule in the less shielded isomer A, and on different sides in the more hindered isomer
B). The isomer A prevails over isomer B, reflecting the possibility of steric control on the dioxygen-binding reaction. Complex 3,
where R1 = R2 = Et, formed the isomers 6A and 6B as 50 : 50. The ratio 4A:4B was 60 : 40 (for methyl-ethyl containing complex
4) and it increased up to 80 : 20 for methyl-isopropyl-containing 5. The molecular structure of isomers 4A and 4B was confirmed
c 2010 John Wiley & Sons, Ltd.
by X-ray analysis. Copyright Keywords: redox-active ligand; o-amidophenolate; antimony(V); dioxygen; NMR spectroscopy; X-ray analysis
Introduction
180
Complexes with redox-active o-quinonato/o-iminoquinonato ligands have been extensively studied during last four decades.
Such compounds are interesting from the viewpoint of not
only fundamental sciense (model objects for the investigation
of magnetic interactions, valence tautomerism, chemical bonding etc.[1] ), but also applied chemistry. For example, copper(II)
and zinc(II) complexes with di-o-iminoquinonato ligands derived
from o-phenylenediamine and 3,5-di-tert-butyl-o-benzoquinone
have been found to be catalysts for aerobic oxidation of primary
alcohols (including ethanol and methanol) to aldehydes.[2a] Copper(II) complex Cu(AP-N-ISQ)(NEt3 ) with tridentate dianion-radical
O,N,O-ligand also catalyzes the oxidation of alcohols to aldehydes
in aerobic conditions.[2b] Bis-o-iminobenzosemiquinonato copper(II) complexes also play the role of effective catalysts for aerobic
oxidation of alcohols to aldehydes, thus modeling enzyme galactose oxidase.[2c] Manganese(IV) complexes with o-iminoquinonato
ligans were shown to mimic enzyme catechol oxidase.[2d,e] Vanadium(IV, V) catecholates are vanadium-containing catalysts of
catechol dioxygenation reactions[2f] .
Complexes with redox-active ligands can also be involved
in reactions of other types.[2d,3] For example, binuclear manganese(IV) complex containing di-o-iminoquinonato ligands
with a m-phenylene bridge is active in the oxidative carbon–carbon coupling reaction of hindered phenols, leading to
diphenoquinones.[2d]
Antimony organometallics is an interesting topic due to the
possibilities of its wide utilization for a variety of chemical,
biochemical and medical purposes.[4 – 6] For example, antimony
complexes with dithio ligands have shown catalytic activity in
different reactions,[4b – d] antimony sulfate is a catalyst in one-pot
synthesis of 2,3-disubstitutedindoles.[4e]
Appl. Organometal. Chem. 2011, 25, 180–189
Medicine uses some antimonial drugs widely; for example,
sodium stibogluconate and meglumine antimonite are used for
the treatment of human visceral leishmaniasis.[5a,b] Antimony
catecholate complex – a derivative of 4,5-dihydroxybenzene-3,
5-disulfonate ligand – was reported to be used as antiparasitic
agent.[5c]
Therefore, the preparation of antimony compounds with redoxactive ligands could be potentially useful from the viewpoint of
fundamental and applied chemistry. Recently, we have found one
more interesting chemical reactivity of antimony complexes: the
combination of redox-active o-amidophenolato and catecholato
ligand with non-transition metal antimony allows transition
metal complex reactivity to be modeled: the reversible binding
of molecular oxygen. Such catecholato or o-amidophenolato
antimony complexes are potential subjects for the investigation of
antibacterial, antifungal and anticancer activities of antimony
compounds.[6c – e] Also, antimony complexes with dioxygenbinding ability hold promise as dioxygen carriers and mild oxidizers
for different processes.
In the present paper we report the investigation of the
dioxygen-binding activity of triphenylantimony(V) complexes with
unsymmetrical 2-alkyl(R1 )-6-alkyl(R2 )-phenyl at nitrogen atom of
∗
Correspondence to: Andrey I. Poddel’sky, G. A. Razuvaev Institute of
Organometallic Chemistry, Russian Academy of Sciences, Tropinina str. 49,
603950 Nizhniy Novgorod, GSP-445, Russia. E-mail: aip@iomc.ras.ru
a G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of
Sciences, Tropinina str. 49, 603950 Nizhniy Novgorod, GSP-445, Russia
b Nizhniy Novgorod State University, Physical Faculty, building 3, Gagarina av.
23, 603950 Nizhniy Novgorod, Russia
c 2010 John Wiley & Sons, Ltd.
Copyright Triphenylantimony(V) o-amidophenolates with unsymmetrical N-aryl group
AP ligand and investigation of the influence of shielding of N-aryl
groups on the spiroendoperoxide composition.
Appl. Organometal. Chem. 2011, 25, 180–189
In the case of dioxygen binding by catecholate/o-amidophenolato
antimony(V) complexes, o-amidophenolato/catecholato dianion
is oxidized by molecular oxygen to o-iminobenzosemiquinonato
radical-anion (electron transfer stage on Scheme 1) while an
oxidation state of central antimony(V) atom is retained.[7,8]
The proposed mechanism of dioxygen binding (Scheme 1)
supposes the coordination of dioxygen molecule to antimony
atom on the first stages. Until now we have not received direct
evidence of the formation of such a primary weak complex. In the
present work we found indirect evidence of the existence of this
stage when we investigated the influence of steric factors on the
stereochemistry of the forming endoperoxide.
The geometrical features of triphenylantimony(V) o-amidophenolato complexes assume that the dioxygen approach to
central antimony atom can be directed to different sides of the
plane of C6 H2 ON moiety in the molecule (Scheme 2), assuming the
formation of geometric isomers of spiroendoperoxide. Scheme 2
shows two variants of O2 attack direction forming by the rotation
of phenyl groups (they are equivalent in the NMR time scale).
This situation was observed on 4,6-di-tert-butyl-N-(2,
6-dialkylphenyl)-o-amidophenolato triphenylantimony(V) complexes;[7,8] in the case of the symmetrical N-(2,6-dialkylphenyl)
group (R1 = R2 in Scheme 2), O2 attacks the central antimony
atom in cases I and II with equal probability. When R1 = R2 and
cases I and II are not equal (Scheme 2), and we should observe the
different probability of formation of isomers from cases I and II. Is
it possible to take control of the isomer formation? To check the
influence of shielding of N-aryl groups on the spiroendoperoxide
composition, we synthesized antimony complexes with unsymmetrical 2-alkyl(R1 )-6-alkyl(R2 )-phenyl at the nitrogen atom of AP
ligand (Scheme 3) and investigated their reaction with dioxygen.
Triphenylantimony(V) o-amidophenolates 1–3 can be easily
prepared from the corresponding o-iminobenzoquinones 1a–3a
(which were synthesized in the accordance with method described
in Abakumov et al.[9] ) and triphenylstibine by the oxidative
addition reaction.[7,8,10] Pure complexes are polycrystalline yelloworange solids which are readily soluble in aromatic solvents, diethyl
ether and THF, and moderately soluble in acetone, aliphatic
solvents (hexane, pentane, etc.). Complexes 1–3 have been
characterized in detail by IR, 1 H and 13 C NMR spectroscopy,
elemental analysis and EI MASS spectroscopy.
The interesting feature of 1 H NMR spectra of complexes 1 and 3
(with ethyl group in N-aryl fragment) is the fact that ethyl protons
form ABX3 system where chemical shift δA = 2.14–2.20 ppm,
δB = 2.55 ppm and δX = 0.94–0.95 ppm, and spin–spin coupling
constants are 2 J(A,B) = 15.0 Hz and 3 J(A,X) = 3 J(B,X) = 7.5 Hz.
The exposition of complexes 1–3 to air allows spiroendoperoxides 4–6 to be obtained as products of dioxygen binding to
initial complexes (Scheme 3). The 1 H and 13 C spectral data on
complexes 4–6 are collected in the Experimental section. We describe 1 H NMR spectroscopic data on o-amidophenolate complex
3 with symmetric N-2,6-diethylphenyl group and its peroxide 6
first, because it will allow us to compare these data with those
ones observed on unsymmetrical complexes 1 and 2.
The 1 H NMR spectra of complex 3 in inert atmosphere and
exposed to air (yielding spiroendoperoxide 6) are shown in Fig. 1.
c 2010 John Wiley & Sons, Ltd.
Copyright wileyonlinelibrary.com/journal/aoc
181
Scheme 1. The proposed mechanism of dioxygen binding by antimony complexes.
Results
A. I. Poddel’sky et al.
Scheme 2. The directions of dioxygen attack on antimony o-amidophenolate.
Scheme 3. The reaction of complexes 1–3 with molecular oxygen.
Scheme 4. The isomers A and B of spiroendoperoxide 4.
182
The singlets from tert-butyl groups protons are shifted from
1.13 and 1.50 ppm (for 3) and to 1.01 and 1.36 ppm (for 6);
doublets from isolated protons (in third and fifth positions) of sixmembered carbon ring C6 H2 ON for 6 have chemical shifts at 5.45
and 6.47 ppm with spin–spin coupling constant 4 J(H,H) = 1.5 Hz
compared with 5.87 and 6.73 ppm with 4 J(H,H) = 2.3 Hz for
initial o-amidophenolate 3. Methyl and methylene protons of
ethyl groups at N-aryl became non-equivalent: methyls give rise
to two triplets (4 J(H,H) = 7.5 Hz) with δ = 0.61 and 0.67 ppm,
methylene protons form multiplets at the region 1.58–2.2 ppm.
Therefore, the NMR spectral features of this dioxygen-bound
complex 6 are consistent with those observed on the
related antimony(V) 4,6-di-tert-butyl-N-(2,6-di-methyl-phenyl/diisopropyl-phenyl)-o-amidophenolates (AP-Me,Me)SbPh3 and (APiPr,iPr)SbPh3 .[7,8b] The spiroendoperoxide 6 [as well as complexes
(AP-Me,Me)SbPh3 and (AP-iPr,iPr)SbPh3 ] has a symmetric N-2,
wileyonlinelibrary.com/journal/aoc
6-dialkylsubstituted phenyl group, and geometrical isomers 6A
and 6B with different positions of peroxo-fragment towards the
plane of the six-membered carbon cycle C6 H2 ON are equivalent and therefore they have identical 1 H and 13 C NMR spectral
characteristics.
In the case of triphenylantimony(V) 4,6-di-tert-butyl-N-(2methyl-6-ethyl-phenyl)-o-amidophenolate, 1, the reaction with
dioxygen also leads to similar changes in 1 H and 13 C NMR
spectra. However, in this case more complicated NMR spectra
have been observed due to different structures of isomers A
and B of spiroendoperoxide 4 (Scheme 3). In 1 H NMR for both
isomers, tBu groups protons give singlets at 1.01 and 1.37 ppm,
and methyl protons of N-aryl appear as two practically overlapping
singlets at 1.45 (4A) and 1.46 (4B) ppm. On the other hand, the
triplets from methyl protons of ethyl groups of these two isomers
are easily distinguishable (0.67 for isomer 4A and 0.61 ppm for
isomer 4B; see Fig. 1, right). Methylene protons of ethyls give
a number of multiplets at 1.60–1.80 and 1.88–2.08 ppm. The
doublets from isolated protons at the third and fifth positions
of C6 H2 ON fragments of isomers are scarcely discernible; the
corresponding chemical shifts are 5.43, 5.44 ppm and 6.47,
6.48 ppm with 4 J(H,H) = 1.5 Hz. Thus, here 1 H NMR spectral
characteristics allow two geometric isomers to be marked out
with different positional relationships of –O–O–fragments and
substituents at the N-aryl group in molecule of spiroendoperoxide
(Scheme 4).
Based on the integral intensities of signals, we can conclude
that the ratio of isomers 4A and 4B in solution is 60 : 40, which can
c 2010 John Wiley & Sons, Ltd.
Copyright Appl. Organometal. Chem. 2011, 25, 180–189
Triphenylantimony(V) o-amidophenolates with unsymmetrical N-aryl group
Figure 1. The 1 H NMR spectra of o-amidophenolates 3 (top, left) and 1 (top, right) and their spiroendoperoxides 6 (bottom, left) and 4 (bottom, right),
correspondingly (CDCl3 , 298 K).
Appl. Organometal. Chem. 2011, 25, 180–189
c 2010 John Wiley & Sons, Ltd.
Copyright wileyonlinelibrary.com/journal/aoc
183
Figure 2. The molecular structure of spiroendoperoxide 4: left, isomer 4A; and right, isomer 4B (H atoms are omitted for clarity).
184
Scheme 5. The reaction of dioxygen exchange between triphenylantimony(V) spiroendoperoxide and manganese complex Mn(ISQ-iPr,iPr)(AP-iPr,iPr)THF.
A. I. Poddel’sky et al.
wileyonlinelibrary.com/journal/aoc
Figure 3. The increasing EPR signal (fourth component) from manganese
peroxo-complex Mn(ISQ-iPr,iPr)2 (O2 )THF in the course of reaction between
Mn(ISQ-iPr,iPr)(AP-iPr,iPr)THF and spiroendoperoxide 6 (toluene, 298 K,
time period is 2 min).
be rationalized by the facts that: (i) the dioxygen attack is directed
by the steric factors of N-aryl group in o-amidophenolates (R 1 = R2
in Scheme 2); and (ii) the formation of isomer 4A (where the steric
repulsion between peroxo-fragment and methyl at N-aryl group is
less than the repulsion between the peroxo-fragment and ethyl in
isomer B) is preferable to the formation of 4B. The strengthening of
steric nonequivalence of alkyl substituents at the second and sixth
positions of N-aryl in complex 2 (methyl and isopropyl groups)
results in the more pronounced predominance of isomer 5A over
isomer 5B when the initial o-amidophenolate 2 is exposed to air.
In this case, the ratio of isomers 5A and 5B in solution is 80 : 20.
Spiroendoperoxides 4–6 lose dioxygen under deaeration or
heating above 50 ◦ C to form initial complexes 1–3, respectively,
like the earlier described spiroendoperoxides.[7,8] The reversible
character of dioxygen binding by complexes 1–3 was confirmed
by NMR spectroscopy monitoring during the repeated cycle
‘aeration–deaeration’.
In order to confirm isomers, the crystal structure of spiroendoperoxide 4 was investigated by single-crystal X-ray analysis. Unfortunately, the quality of the crystals was not good
enough. However, crystals contain both isomers 4A and 4B.
Figure 2 shows the 4A (left) and 4B (right) isomers. The central antimony atoms are in a distorted octahedral environment.
Both the isomers 4A and 4B display the same structural features including a breaking of the aromatic ring C(1–6) as in
the cases of spiroendoperoxides derived from 4,6-di-tert-butyl-N(2,6-dialkylphenyl)-o-amidophenolato triphenylantimony(V) complexes (AP-R,R)SbPh3 (R = alkyl is isopropyl or methyl).[7,8b] The
carbon ring C(1–6) looses the aromaticity under dioxygen addition
because the C(1) atom becomes tetrahedral and sp3 -hibridized.
The bonds N(1)–C(2) in 4A and 4B [1.310(4) and 1.275(3) Å]
are close to those observed in other spiroendoperoxides[7,8b]
and have double (imino) character being much shorter than
ordinary N(1)–C(15) distances [1.434(3) and 1.444(3) Å]; bonds
C(3)–C(4) and C(5)–C(6) are short and display a double bond
type, while C(2)–C(3) and C(4)–C(5) are long ordinary bonds.
The donor-acceptor Sb(1)–N(1) bonds in both isomers [2.500(3)
and 2.425(2) Å] are the same as in symmetrical spiroendoperoxides (2.425–2.480 Å).[7,8b] A small difference between Sb-CPh as
well as Sb–O distances is observed for 4A and 4B [for instance,
c 2010 John Wiley & Sons, Ltd.
Copyright Appl. Organometal. Chem. 2011, 25, 180–189
Triphenylantimony(V) o-amidophenolates with unsymmetrical N-aryl group
Sb–CPh varies in the range of 2.120(2)–2.137(3) Å in 4A, and
2.136(2)–2.178(2) Å in 4B]. The peroxo-bonds O(2)–O(3) in isomers 4A and 4B are equal within experimental error [1.468(3)
and 1.468(2) Å, respectively]. The peroxo-bonds O–O in symmetrical complexes are the same [1.461(3) Å in spiroendoperoxide
of (AP-iPr,iPr)SbPh3 and 1.466(2) in spiroendoperoxide of (APMe,Me)SbPh3 ],[7,8b] and endoperoxide 3,3-dihidro-5,5-dimethyl3,3,3-triphenyl-1,2,4,3-trioxastibolane has an O–O distance of
1.468 Å.[11]
The interaction of dioxygen with transition metal complexes is well known.[12] Some of o-iminosemiquinonato/oamidophenolato transition metal complexes were also shown
to react with molecular oxygen to form different derivatives.
We found that pentacoordinated manganese complex with
sterically hindered 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-oiminobenzosemiquinonato ligands, Mn(ISQ-iPr,iPr)(AP-iPr,iPr)THF,
is also able to reversible dioxygen binding forming manganese
peroxo-complex Mn(ISQ-iPr,iPr)2 (O2 )THF.[13] The initial complex
has a quadruplet spin state and does not reveal an isotropic
spectrum EPR in solution at ambient temperature. At the same
time, spin state of peroxo-complex is doublet and this complex shows well-resolved EPR {sextet (1 : 1:1 : 1:1 : 1) of quintets
(1 : 2:3 : 2:1) due to hyper-fine coupling of unpaired electron with
one manganese [Ai (55 Mn) = 106–107 G] and two equal nitrogen [Ai (14 N1) = Ai (14 N2) = 3.5 G] nuclei}.[13] This fact allows
us to take control on the process using EPR technique. Therefore, manganese complex Mn(ISQ-iPr,iPr)(AP-iPr,iPr)THF can be
used as the dioxygen trap. We found that the addition of manganese complex to solutions of spiroendoperoxides [described
in this paper (4–6) and reported in the literature[7,8b] ] results
in the appearance of an EPR signal from manganese peroxocomplex observed in Abakumov et al.[13] The intensity of EPR
spectrum increases with time, showing the presence of a reaction
between Mn(ISQ-iPr,iPr)(AP-iPr,iPr)THF and spiroendoperoxides
(Scheme 5). Figure 3 shows the increasing EPR signal (only the
fourth component of EPR spectrum is shown) with time (time range
is 6–60 min with a time interval of 2 min). On the other hand, the
treatment of manganese peroxo-complex Mn(ISQ-iPr,iPr)2(O2 )THF
with triphenylantimony(V) o-amidophenolate causes quite a
slow decrease in EPR spectrum from manganese complex. EPR
experiment shows that the reaction of dioxygen exchange
between manganese and antimony complexes is reversible
and can be realized in both directions. We observed no visible differences in the behavior of antimony complexes with
different N-aryl group (symmetrical or unsymmetrical) in this
reaction.
Therefore, triphenylantimony(V) o-amidophenolate complexes
1–3 can serve as traps of dioxygen while spiroendoperoxides 4–6
as well as the spiroendoperoxides described earlier are dioxygen
carriers and can be used as the source of dosated amounts
of O2 .
Conclusion
Appl. Organometal. Chem. 2011, 25, 180–189
Experimental
Materials and Physical Measurements
All manipulations were carried out under an air-free atmosphere.
The starting reagents were purchased from Aldrich and solvents
were purified using standard technique.[14] A Bruker Avance
DPX-200 spectrometer was used for recording the 1 H, 13 C and
13 C DEPT NMR spectra. Chemical shifts for 1 H and 13 C spectra
were referenced internally according to the residual solvent
resonances and reported relative to TMS; CDCl3 was used as
the solvent. Infrared spectra were recorded on a Perkin–Elmer FTIR spectrometer in Nujol mulls and reported in cm−1 . EPR spectra
were monitored using an X-band EPR spectrometer (Bruker EMX)
in toluene at a temperature of 298 K.
Synthesis of Ligands
o-Iminobenzoquinones 1a–3a were prepared from 3,5-di-tertbutyl-o-benzoquinone and corresponding 2,6-substituted aniline
in the accordance with method described in Abakumov et al.[9]
4,6-Di-tert-butyl-N-(2-methyl-6-ethylphenyl)-o-iminobenzoquinone
IBQ-Me,Et (1a)
IR (nujol, v, cm−1 ): 1660s, 1627s, 1553s, 1280s, 1249s, 1197s, 1101m,
1084 w, 1075 w, 1054 w, 1025m, 967m, 933 w, 897s, 872 w, 834 w,
802m, 785 w, 762s, 648 w, 611 w, 480 w.
1 H NMR (200 MHz, δ, ppm): 1.07 (s, 9H, tBu), 1.08 (t, 3 J
(H,H) =
7.5 Hz, 3H, CH3 of Et), 1.34 (s, 9H, tBu), 1.95 (s, 3H, Me), 2.29
(m, 2 J(H,H) = 14.8 Hz, 3 J(H,H) = 7.5 Hz, 1H, CH2 of Et), 2.38
(m, 2 J(H,H) = 14.8 Hz, 3 J(H,H) = 7.5 Hz, 1H, CH2 of Et), 5.84 (d,
4J
(H,H) = 2.2 Hz, 1H, C6 H2 ), 6.93–7.12 (m, 4H, 3H of C6 H3 and 1H of
C6 H2 ).
13 C NMR (50.3 MHz, δ, ppm): 13.95 (CH CH ), 18.20 (CH ), 24.51
3
2
3
(CH3 CH2 ), 28.39 [C(CH3 )3 ], 29.38 [C(CH3 )3 ], 35.18 [C(CH3 )3 ], 35.30
[C(CH3 )3 ], 114.37 (CH of C6 H2 ), 124.13 (p-CH of C6 H3 ), 124.40 [oC(Me) of C6 H3 ], 125.78 (m-CH of C6 H3 ), 127.60 (m-CH of C6 H3 ),
131.44 [o-C(Et) of C6 H3 ], 133.77 (CH of C6 H2 ), 147.60 (i-C of C6 H3 ),
148.97 [C(tBu) of C6 H2 ], 153.26 [C(tBu) of C6 H2 ], 157.58 (C N),
183.79 (C O).
13 1
C{ H} NMR (50.3 MHz, δ, ppm): 13.95, 18.20, 24.51, 28.39,
29.38, 114.37, 124.13, 125.78, 127.60, 133.77.
4,6-Di-tert-butyl-N-(2-methyl-6-isopropylphenyl)-oiminobenzoquinone IBQ-Me, iPr (2a)
IR (nujol, v, cm−1 ): 1673s, 1629s, 1582m, 1562m, 1409s, 1363s,
1304 w, 1281 w, 1267m, 1239s, 1199s, 1181m, 1150 w, 1117 w,
c 2010 John Wiley & Sons, Ltd.
Copyright wileyonlinelibrary.com/journal/aoc
185
We designed and synthesized new o-iminobenzoquinones containing N-aryl groups unsymmetrically substituted in the second and sixth positions and prepared triphenylantimony(V)
o-amidophenolates of (AP-R1 ,R2 )SbPh3 type using these oiminoquinones. o-Amidophenolates react with molecular oxygen
to give different geometrical isomers of spiroendoperoxides with
different position of peroxo-fragment towards O,O ,N-coordinated
ligand plane (the less shielded isomer A where the -O-O- and Me
group are on the same side of spiroendoperoxide molecule, and
the more shielded isomer B where -O-O- and Me groups occupy different sides of the molecule). In the case of symmetrical
N-aryl (2,6-di-methyl-phenyl, 2,6-di-ethyl-phenyl, 2,6-di-isopropylphenyl), the ratio of isomers A : B is 50 : 50, while for 2-methyl6-ethyl-phenyl containing o-amidophenolate, A : B is 60 : 40; for
2-methyl-6-isopropyl-phenyl containing o-amidophenolate, A : B
is 80 : 20. This fact allows us to suppose that the steric control
on the reaction of antimony o-amidophenolates with molecular
oxygen can be performed by using different alkyl substituents at
the N-aryl group of o-amidophenolate.
A. I. Poddel’sky et al.
1102 w, 1094 w, 1052 w, 1024 w, 997m, 983 w, 968 w, 948 w,
932 w, 898m, 878m, 829m, 801 w, 778m, 759m, 734m, 653 w,
617 w.
1 H NMR (200 MHz, δ, ppm): 1.03 (d, 3 J
(H,H) = 6.8 Hz, 3H, CH3 of
iPr), 1.08 (s, 9H, tBu), 1.17 (d, 3 J(H,H) = 6.8 Hz, 3H, CH3 of iPr), 1.35 (s,
9H, tBu), 1.94 (s, 3H, Me), 2.74 (sept., 3 J(H,H) = 6.8 Hz, 1H, CH of iPr),
5.85 (d, 4 J(H,H) = 2.1 Hz, 1H, C6 H2 ), 6.94–7.20 (m, 4H, 3H of C6 H3
and 1H of C6 H2 ).
13 C NMR (50.3 MHz, δ, ppm): 18.18 (CH ), 23.23 [CH(CH ) ], 23.46
3
3 2
[CH(CH3 )2 ], 28.01 [CH(CH3 )2 ], 28.38 [C(CH3 )3 ], 29.40 [C(CH3 )3 ], 35.21
[C(CH3 )3 ], 35.30 [C(CH3 )3 ], 114.46 (CH of C6 H2 ), 122.93 (m-CH of
C6 H3 ), 124.21 (p-CH of C6 H3 ), 124.30 [o-C(Me) of C6 H3 ], 127.58
(m-CH of C6 H3 ),136.00 [o-C(iPr) of C6 H3 ], 133.83 (CH of C6 H2 ),
146.50 (i-C of C6 H3 ), 148.95 [C(tBu) of C6 H2 ], 153.02 [C(tBu) of
C6 H2 ], 157.80 (C N), 183.79 (C O).
13 C{1 H} NMR (50.3 MHz, δ, ppm): 18.18, 23.23, 23.46, 28.01,
28.38, 29.40, 114.46, 122.93, 124.21, 127.58, 133.83.
4,6-Di-tert-butyl-N-(2,6-diethylphenyl)-o-iminobenzoquinone
IBQ-Et,Et (3a)
IR (nujol, v, cm−1 ): 1662s, 1627s, 1572 w, 1556m, 1280s, 1269m,
1247s, 1192s, 1106 w, 1081 w, 1063 w, 1025 w, 967 w, 931 w,
897s, 880m, 835 w, 803m, 786m, 760s, 734 w, 647 w, 614 w,
482 w.
1 H NMR (200 MHz, δ, ppm): 1.07 (s, 9H, tBu), 1.08 (t, 3 J
(H,H) =
7.5 Hz, 6H, 2 CH3 of 2 Et), 1.34 (s, 9H, tBu), 2.25 (m, 2 J(H,H) = 13.7 Hz,
3
J(H,H) = 7.5 Hz, 2H, 2 CH2 of 2 Et), 2.34 (m, 2 J(H,H) = 13.7 Hz,
3J
4
(H,H) = 7.5 Hz, 2H, 2 CH2 of 2 Et), 5.84 (d, J(H,H) = 2.2 Hz, 1H,
4
C6 H2 ), 6.99 (d, J(H,H) = 2.1 Hz, 1H, C6 H2 ), 6.98–7.18 (m, 3H, 3H of
C6 H3 ).
13 C NMR (50.3 MHz, δ, ppm): 13.90 (CH CH ), 24.40 (CH CH ),
3
2
3
2
28.39 [C(CH3 )3 ], 29.40 [C(CH3 )3 ], 35.20 [C(CH3 )3 ], 35.32 [C(CH3 )3 ],
114.50 (CH of C6 H2 ), 124.26 (p-CH of C6 H3 ), 125.64 (m-CH of C6 H3 ),
130.77 [o-C(Et) of C6 H3 ], 133.80 (CH of C6 H2 ), 147.17 (i-C of C6 H3 ),
148.96 [C(tBu) of C6 H2 ], 153.10 [C(tBu) of C6 H2 ], 157.84 (C N),
183.80 (C O).
13 1
C{ H} NMR (50.3 MHz, δ, ppm): 13.90, 24.40, 28.39, 29.40,
114.50, 124.26, 125.64, 133.77.
Synthesis of Complexes
4,6-Di-tert-butyl-N-(2-methyl-6-ethyl-phenyl)-oamidophenolato)triphenylantimony(V) (1)
186
o-Iminobenzoquinone 1a (0.290 g, 0.86 mmol) in toluene (20 ml)
was added with extensive stirring to a triphenylstibine (0.305 g,
0.86 mmol) in toluene (20 ml). The solution color changed from
cherry-red to bright yellow. After the addition was complete,
solvent toluene was removed by evaporation in vacuo and residue
was dissolved in warm hexane. The storage of this solution
overnight allowed the product precipitation as a bright yellow
crystalline powder. The yield of 1 was 0.545 g (91.6%). EI-MS (m/z):
689, 691 ([M]+ ). IR (nujol, v, cm−1 ): 1565 m, 1508 w, 1463 s, 1444 s,
1433 s, 1415 m, 1377 s, 1366 m, 1336 m, 1304 w, 1288 m, 1265 m,
1247 s, 1200 w, 1183 w, 1162 w, 1157 w, 1117 w, 1100 w, 1067 m,
1023 w, 993 m, 921 w, 898 m, 857 m, 828 m, 786 m, 758 w, 730 s,
694 m, 669 m, 656 m, 616 w, 604 w, 587 w, 570 w, 547 m, 537 m,
516 s, 489 m, 471 w, 450 m, 420 m.
1 H NMR (CDCl , δ, ppm): 0.94 (t, 3 J
3
(H,H) = 7.5 Hz, 3H, CH3 of Et),
1.14 and 1.50 (each s, each 9H, tBu), 2.00 (s, 3H, Me), 2.14 and 2.55
(each m, 3 J(H,H) = 7.5 Hz and 2 J(H,H) = 15.0 Hz, each 1H, CH2 of Et),
wileyonlinelibrary.com/journal/aoc
5.88 and 6.74 (each d, 4 J(H,H) = 2.3 Hz, each 1H, C6 H2 ), 6.64–6.82
(m, 3H, C6 H3 ), 7.18–7.40 (m, 9H, SbPh3 ), 7.45–7.58 (m, 6H, SbPh3 ).
13 C NMR (CDCl , δ, ppm): 14.27 (CH of Et), 18.74 (CH ), 24.33
3
3
3
(CH2 of Et), 29.91 and 31.76 (CH3 of tBu), 34.28 and 34.75 (C of
tBu), 106.79 (CH of C6 H2 ), 111.69 (CH of C6 H2 ), 125.46 (CH of C6 H3 ),
126.20 (CH of C6 H3 ), 127.65 (CH of C6 H3 ), 128.27 (Ph), 130.24 (Ph),
131.22 (C Ar), 135.00 (Ph), 135.18 (C Ar), 137.70 (C Ar), 138.65 (C
Ar), 138.91 (Ph), 139.05 (C Ar), 144.25 (C–N Ar), 146.54 (C–O Ar).
Anal. calcd for C41 H46 NOSb (690.57): C, 71.31; H, 6.71; N, 2.03; Sb,
17.63. Found: C, 71.17; H, 6.57; N, 2.12; Sb, 17.80.
4,6-Di-tert-butyl-N-(2-methyl-6-isopropyl-phenyl)-oamidophenolato)triphenylantimony(V) (2)
Complex 2 was prepared by the reaction of triphenylstibine (0.363 g, 1.03 mmol) and 4,6-di-tert-butyl-N-(2-methyl-6isopropylphenyl)-o-iminobenzoquinone 2a (0.361 g, 1.03 mmol)
using the same method as for 1. The product was isolated as
yellow powder from hexane. EI-MS (m/z): 703, 705 ([M]+ ). IR (nujol,
v, cm−1 ): 1416 s, 1377 s, 1361 m, 1333 m, 1304 w, 1288 s, 1248 s,
1201 w, 1180 w, 1121 w, 1101 w, 1065 m, 1050 w, 1026 w, 991s,
965 w, 922 w, 897 m, 876 w, 855 m, 828 m, 781 m, 770 m, 759 w,
732 s, 693 m, 671 m, 657 m, 609 w, 593 w, 570 w, 545 w, 532 m,
515 s, 488 m, 459 m, 452 m, 446 m.
1 H NMR (CDCl , δ, ppm): 0.78 and 0.91 (each d, 3 J
3
(H,H) = 6.9 Hz,
each 3H, 2 CH3 of iPr), 1.13 and 1.48 (each s, each 9H, tBu), 2.02 (s,
3H, Me), 3.05 (quint, 3 J(H,H) = 6.9 Hz, 1H, CH of iPr), 5.88 and 6.72
(each d, 4 J(H,H) = 2.2 Hz, each 1H, C6 H2 ), 6.90–7.20 (m, 3H, C6 H3 ),
7.20–7.38 (m, 9H, Ph), 7.45–7.58 (m, 6H, Ph).
13 C NMR (CDCl , δ, ppm): 18.99 (CH ), 21.98 and 25.89 (CH of
3
3
3
iPr), 28.32 (CH of iPr), 29.89 and 31.73 (CH3 of tBu), 34.27 and 34.73
(C of tBu), 107.52 (CH of C6 H2 ), 111.63 (CH of C6 H2 ), 123.28 (CH
of C6 H3 ), 126.47 (CH of C6 H3 ), 127.59 (CH of C6 H3 ), 128.27 (Ph),
130.18 (Ph), 131.22 (C Ar), 135.06 (Ph), 135.59 (C Ar), 137.45 (C Ar),
138.66 (C Ar), 138.75 (C Ar), 139.10 (Ph), 146.52 (C–N Ar), 149.02
(C–O Ar). Anal. calcd for C42 H48 NOSb (704.60): C, 71.59; H, 6.87; N,
1.99; Sb, 17.28. Found: C, 71.40; H, 6.99; N, 1.90; Sb, 17.38.
4,6-Di-tert-butyl-N-(2,6-diethyl-phenyl)-oamidophenolato)triphenylantimony(V) (3)
Complex 3 was prepared by the reaction of triphenylstibine
(0.337 g, 0.95 mmol) and 4,6-di-tert-butyl-N-(2,6-diethylphenyl)o-iminobenzoquinone 3a (0.334 g, 0.95 mmol) using the same
method as for 1. The target product was isolated as bright yellow
crystals from hexane.
EI-MS (m/z): 703, 705 ([M]+ ). IR (nujol, v, cm−1 ): 1564 w, 1464 s,
1417 w, 1377 s, 1353 w, 1334 m, 1305 w, 1289 w, 1266 w, 1245 m,
1200 w, 1180 w, 1167 w, 1120 w, 1104 w, 1071 w, 1062 w, 1026 w,
1019 w, 992 m, 965 w, 920 w, 898 w, 853 w, 828 w, 800 w, 794 w,
770 w, 757 w, 724 m, 691 w, 667 w, 655 w, 544 w, 530 w, 510 w,
487 w, 451 m, 444 m.
1 H NMR (CDCl , δ, ppm): 0.95 (t, 3 J
3
(H,H) = 7.5 Hz, 6H, 2CH3 of 2
Et), 1.13 and 1.50 (each s, each 9H, 2 tBu), 2.20 and 2.55 (each m,
4J
2
(H,H) = 7.5 Hz and J(H,H) = 15.0 Hz, each 2H, 2CH2 of 2 Et), 5.87
and 6.73 (each d, 4 J(H,H) = 2.3 Hz, each 1H, C6 H2 ), 6.68–6.88 (m,
3H, C6 H3 ), 7.18–7.38 (m, 9H, SbPh3 ), 7.46–7.62 (m, 6H, SbPh3 ).
13 C NMR (CDCl , δ, ppm): 14.01 (CH of Et), 24.12 (CH of Et),
3
3
2
29.90 and 31.74 (CH3 of tBu), 34.28 and 34.74 (C of tBu), 107.21
(CH of C6 H2 ), 111.58 (CH of C6 H2 ), 125.12 (2CH of C6 H3 ), 126.36
(CH of C6 H3 ), 128.25 (Ph), 130.21 (Ph), 131.16 (C Ar), 134.13 (C Ar),
135.03 (Ph), 135.78 (C Ar), 137.53 (C Ar), 138.94 (Ph), 143.98 (C–N
c 2010 John Wiley & Sons, Ltd.
Copyright Appl. Organometal. Chem. 2011, 25, 180–189
Triphenylantimony(V) o-amidophenolates with unsymmetrical N-aryl group
Ar), 146.45 (C–O Ar). Anal. calcd for C42 H48 NOSb (704.60): C, 71.59;
H, 6.87; N, 1.99; Sb, 17.28. Found: C, 71.65; H, 6.80; N, 2.05; Sb, 17.40.
Spiroendoperoxide [L-Me,Et(O2 )]SbPh3 (4)
A sample of o-amidophenolate 1 was dissolved in toluene and
the solution was stored in air. The slow evaporation of solvent
allowed the precipitation of an orange-yellow powder of 4 in a
yield of >90%. The recrystallization of this powder from acetone
gave crystals suitable for single-crystal X-ray diffraction analysis.
4A: 1 H NMR (CDCl3 , δ, ppm): 0.67 (t, 3 J(H,H) = 7.5 Hz, 3H, CH3 of
Et), 1.02 and 1.37 (each s, each 9H, tBu), 1.45 (s, 3H, Me), 1.56–2.10
(each m, 3 J(H,H) = 7.5 Hz, each 1H, CH2 of Et), 5.42 and 6.46 (each
d, 4 J(H,H) = 1.5 Hz, each 1H, C6 H2 ), 6.8–7.1 (m, 3H, C6 H3 ), 7.0–8.1
(mults, 15H, SbPh3 ).
13 C NMR (CDCl , δ, ppm): 13.86 (CH of Et), 17.29 (CH ), 23.74
3
3
3
(CH2 of Et), 28.37 and 30.59 (CH3 of tBu), 35.71 and 37.13 (C
of tBu), 96.34 [quaternary C(OO)O], 108.04 and 122.41 [CH of
C6 H2 O3 N]; 125.35, 125.44 and 128.17 (CH of C6 H3 ); 128.20 (Ph),
129.44 (Ph), 131.82 (C of C6 H3 ), 134.45 (Ph), 134.82 (Ph), 136.02 (C
of C6 H3 ), 142.85 (C–N of C6 H3 ), 155.17 [C of C6 H2 O3 N], 159.71 [C
of C6 H2 O3 N], 168.50 (C N).
4B: 1 H NMR (CDCl3 , δ, ppm): 0.61 (t, 3 J(H,H) = 7.5 Hz, 3H, CH3 of
Et), 1.02 and 1.37 (each s, each 9H, tBu), 1.46 (s, 3H, Me), 1.56–2.10
(each m, 3 J(H,H) = 7.5 Hz, each 1H, CH2 of Et), 5.43 and 6.48 (each
d, 4 J(H,H) = 1.5 Hz, each 1H, C6 H2 ), 6.8–7.1 (m, 3H, C6 H3 ), 7.0–8.1
(mults, 15H, SbPh3 ).
13 C NMR (CDCl , δ, ppm): 13.50 (CH of Et), 18.12 (CH ), 22.16 (CH
3
3
3
2
of Et), 28.37 and 30.65 (CH3 of tBu), 35.79 and 37.13 (C of tBu), 96.19
[quaternary C(OO)O], 107.93 and 122.46 (CH of C6 H2 O3 N); 125.37,
126.03 and 127.35 (CH C6 H3 ), 128.20 (Ph), 129.44 (Ph), 131.59 (C
of C6 H3 ), 134.45 (Ph), 134.82 (Ph), 137.55 (C of C6 H3 ), 142.97 (C–N
of C6 H3 ), 155.14 (C of C6 H2 O3 N), 159.67 (C of C6 H2 O3 N), 168.43
(C N).
Spiroendoperoxide [L-Et,Et(O2 )]SbPh3 (6)
A sample of 6 was prepared from 3 by the same method as
described for 4. Spiroendoperoxide 6A and 6B: 1 H NMR (CDCl3 , δ,
ppm): 0.61 and 0.67 (each t, 3J(H,H) = 7.5 Hz, each 3H, 2 CH3 of 2 Et),
1.01 and 1.36 (each s, each 9H, tBu), 1.58–2.20 (m, 3 J(H,H) = 7.5 Hz,
4H, 2 CH2 of 2 Et), 5.45 and 6.47 (each d, 4 J(H,H) = 1.5 Hz, each 1H,
C6 H2 ), 6.8–7.15 (m, 3H, C6 H3 ), 7.20–7.60 (m, 9H, Ph), 7.70–8.35 (m,
6H, Ph).
13 C NMR (CDCl , δ, ppm): 13.42 and 13.86 (CH of Et), 22.02 and
3
3
23.70 (CH2 of Et), 28.37 and 30.66 (CH3 of tBu), 35.77 and 37.14
(C of tBu), 96.18 [quaternary C(OO)O], 108.38 and 122.45 (CH of
C6 H2 O3 N); 125.22, 125.55 and 125.91 (CH of C6 H3 ), 128.18 (Ph),
129.47 (Ph), 131.60 (C of C6 H3 ), 134.46 (Ph), 135.02 (Ph), 137.39 (C
of C6 H3 ), 142.41 (C–N of C6 H3 ), 155.09 (C of C6 H2 O3 N), 159.31 (C
of C6 H2 O3 N), 168.86 (C N).
Reactions with manganese complexes: Mn(ISQ-iPr,iPr)(APiPr,iPr)THF was synthesized as described in Abakumov et al.[13a]
The sample of this complex was dissolved in deaerated toluene in
ampoule equipped with thin capillary tube for EPR experiment and
this solution was EPR-silent. After that, a sample of spiroendoperoxide 4–6 or derived from (AP-R,R)SbPh3 (R = iPr, Me) was added
to this solution and then EPR spectra were recorded every 2 min for
Table 1. Summary of crystal and refinement data
Formula
Formula weight
Temperature, K
Wavelength, Å
Crystal system
Space group
Unit cell dimensions
Spiroendoperoxide [L-Me,iPr(O2 )]SbPh3 (5)
Appl. Organometal. Chem. 2011, 25, 180–189
Volume, Å 3
Z
Calculated density, mg m−3
Absorption coefficient, mm−1
F(000)
Crystal size, mm
Theta range for data collection
Limiting indices
Reflections collected/unique
Completeness to θ
Max. and min. transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F 2
Final R indices [I > 2σ (I)]
R indices (all data)
Largest difference peak/hole, e A−3
c 2010 John Wiley & Sons, Ltd.
Copyright wileyonlinelibrary.com/journal/aoc
187
A sample of 5 was prepared from 2 by the same method as
described for 4.
5A: 1 H NMR (CDCl3 , δ, ppm): 0.39 and 0.75 (each d, 3 J(H,H) =
6.8 Hz, each 3H, 2 CH3 of iPr), 1.01 and 1.36 (each s, each 9H, tBu),
1.41 (s, 3H, Me), 2.57 (quint, 3 J(H,H) = 6.8 Hz, 1H, CH of iPr), 5.44
and 6.47 (each d, 4 J(H,H) = 2.2 Hz, each 1H, C6 H2 ), 6.80–7.20 (m,
3H, C6 H3 ), 7.20–7.60 (m, 9H, Ph), 7.70–8.30 (m, 6H, Ph).
13
C NMR (CDCl3 , δ, ppm): 17.44 (CH3 ), 21.17 and 25.10 (CH3 of
iPr), 28.29 (CH of iPr), 28.36 and 30.61 (CH3 of tBu), 35.71 and 37.14
(C of tBu), 96.29 [quaternary C(OO)O], 108.23 and 122.39 (CH of
C6 H2 O3 N); 122.82, 125.59 and 128.05 (CH of C6 H3 ), 128.10 (Ph),
129.45 (Ph), 131.78 (C of C6 H3 ), 134.46 (Ph), 134.72 (Ph), 140.98 (C
of C6 H3 ), 141.94 (C–N of C6 H3 ), 155.17 (C of C6 H2 O3 N), 159.54 (C
of C6 H2 O3 N), 168.68 (C N).
5B: 1 H NMR (CDCl3 , δ, ppm): 0.01 and 0.84 (each d, 3 J(H,H) =
6.8 Hz, each 3H, 2 CH3 of iPr), 1.01 and 1.36 (each s, each 9H, tBu),
1.93 (s, 3H, Me), 2.91 (quint, 3 J(H,H) = 6.8 Hz, 1H, CH of iPr), 5.48
and 6.51 (each d, 4 J(H,H) = 2.2 Hz, each 1H, C6 H2 ), 6.80–7.20 (m,
3H, C6 H3 ), 7.20–7.60 (m, 9H, Ph), 7.70–8.30 (m, 6H, Ph).
13 C NMR (CDCl , δ, ppm): 18.39 (CH ), 21.83 and 24.90 (CH of
3
3
3
iPr), 26.38 (CH of iPr), 28.36 and 30.82 (CH3 of tBu), 35.89 and 37.15
(C of tBu), 96.11 [quaternary C(OO)O], 108.52 and 122.65 (CH of
C6 H2 O3 N); 124.38, 125.67 and 127.32 (CH of C6 H3 ), 128.10 (Ph),
129.45 (Ph), 131.60 (C of C6 H3 ), 134.46 (Ph), 134.72 (Ph), 142.35 (C
of C6 H3 ), 142.71 (C–N of C6 H3 ), 155.02 (C of C6 H2 O3 N), 159.02 (C
of C6 H2 O3 N), 168.15 (C N).
C41 H46 NO3 Sb
721.06
100(2)
0.71073
Trilinic
P1
a, Å
10.8020(2)
b, Å
12.1954(3)
c, Å
15.1479(4)
α, deg 96.412(2)
β, deg 107.685(2)
γ , deg 107.145(2)
1771.77(7)
2
1.352
0.817
745.0
0.20 × 0.16 × 0.15
3.47–30.51◦
−15 ≤ h ≤ 15
−17 ≤ k ≤ 17
−21 ≤ l ≤ 21
18 701/16 117
[R(int) = 0.0168]
θ = 30.51◦ , 98.8%
1.0 and 0.88232
Full-matrix
least-squares on F 2
18 908/3/724
0.18
R1 = 0.0277,
wR2 = 0.0608
R1 = 0.0320,
wR2 = 0.0666
1.278/−1.051
A. I. Poddel’sky et al.
Table 2. The selected bond lengths in isomers 4A and 4B
Bond length, Å
Isomer 4A
Isomer 4B
Sb(1)–O(1)
Sb(1)–O(2)
Sb(1)–C(24)
Sb(1)–C(30)
Sb(1)–C(36)
Sb(1)–N(1)
O(1)–C(1)
O(3)–C(1)
O(2)–O(3)
N(1)–C(2)
N(1)–C(15)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
C(6)–C(1)
2.0376(18)
2.0800(19)
2.128(3)
2.120(2)
2.137(3)
2.500(3)
1.396(3)
1.449(2)
1.468(3)
1.310(4)
1.434(4)
1.520(4)
1.420(4)
1.303(4)
1.499(4)
1.307(4)
1.519(3)
2.0133(15)
2.0734(15)
2.142(3)
2.178(2)
2.136(2)
2.475(2)
1.350(3)
1.480(2)
1.468(2)
1.275(3)
1.444(3)
1.543(3)
1.463(4)
1.395(3)
1.442(4)
1.368(4)
1.523(3)
1 h. To perform a reaction between manganese peroxo-complex
Mn(ISQ-iPr,iPr)2 (O2 )THF and o-amidophenolate (Cat-R1 ,R2 )SbPh3
1–3 or (AP-R,R)SbPh3 (R = iPr, Me), manganese complex Mn(ISQiPr,iPr)(AP-iPr,iPr)THF and the corresponding o-amidophenolate
were dissolved in deaerated toluene. After rapid addition of
small amounts of dioxygen, the manganese complex transformed completely to peroxo-complex Mn(ISQ-iPr,iPr)2 (O2 )THF
(its reaction rate with dioxygen is far greater than that for antimony complexes) and EPR monitoring was performed using this
solution.
X-ray Diffraction Studies
X-ray diffraction data for 4 were collected using an Oxford Diffraction (Gemini S) diffractometer with graphite monochromated,
MoKα radiation (λ = 0.71073 Å) and with CCD detector Sapphire III in the ω-scan mode (hemisphere, θ = 3.47–30.51◦ ) at
a temperature of 100 K. The crystal structure was solved by direct methods (SHELX97)[15] and refined by the full matrix method
(WINGX and SHELX97).[16] The reflection data were processed using the multi-scan absorption correction algorithm:[17] primary
atom site location, structure-invariant direct methods; secondary
atom site location, difference Fourier map. Most of the H atoms
were placed in calculated positions and refined in the ‘ridingmodel’ [Uiso(H) = 1.2Ueq (carbon) for aromatic hydrogen and
1.5Ueq (carbon) for alkyl hydrogen], and the another part was
located from Fourier synthesis and refined isotropically.[15] The
minimal R1 -factor was 0.0277. No solvent molecules were found
in crystals of 4. Table 1 summarizes the crystal data and some
details of the data collection and refinement for 4. The selected
bond distances and angles for isomers 4A and 4B are given in
Table 2.
Acknowledgements
188
We are grateful to the Russian Foundation for Basic Research
(grants 10-03-00921) and the President of Russian Federation
(grants NSh-7065.2010.3 and MK-1286.2009.3) for financial support of this work. This work was carried out as part of the FSP
wileyonlinelibrary.com/journal/aoc
‘Scientific and Scientific–Pedagogical Cadres of Innovation Russia’
for 2009-2013 (GK-P982 from 27 May 2010).
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triphenylantimony, reversible, group, amidophenolates, dioxygen, binding, aryl, unsymmetric
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