Reaction of the framework 3d-organometallosiloxanes with acetylacetone

Article abstract of DOI:10.1007/s11172-010-0248-3

A reaction of acetylacetone with the framework sandwich-type metallosiloxanes (MOS) of general formula [PhSiO₂]₆M ₆[PhSiO₂]₆, where M = Cu, Ni, Mn, was studied by GPC, ¹H and ²⁹Si NMR spectroscopy, X-ray diffraction, elemental and functional analysis. The reaction involved replacement of the metal atoms with the hydrogen atoms and is accompanied by the formation of the corresponding chelate complexes M(acac)₂. Displacement of the metal from the framework MOS leads to the destruction of molecular skeleton and formation of phenylsiloxanes containing Si-OH groups. The yield and composition of the reaction products considerably depend on the nature of the metal in [PhSiO₂]₆M₆[ThSiO₂]₆. A selective substitution of the metal leads to the stereoregular hexahydroxyhexaphenylcyclohexasiloxane, [PhSiO(PH)]₆, cis-isomer. The structure and composition of the crystalline hexahydroxyhexaphenylcyclohexasiloxane obtained were confirmed by ²⁹Si NMR spectroscopy, X-ray diffraction study, and functional analysis, while its TMS derivative was studied with ¹H NMR spectroscopy and GPC. Using a framework manganese phenylsiloxane as an example, a reversible character of the process has been established and an alternative synthesis of this compound from hexahydroxyhexaphenylcyclohexasiloxane and Mn(acac)₂ has been accomplished for the first time.

Full text of DOI:10.1007/s11172-010-0248-3

Russian Chemical Bulletin, International Edition, Vol. 59, No. 7, pp. 1369—1375, July, 2010
1369
Reaction of the framework 3dꢀorganometallosiloxanes
with acetylacetone
N. V. Sergienko,a N. V. Cherkun,a V. D. Myakushev,b A. A. Korlyukov,a and B. G. Zavina
aA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085. Eꢀmail: zavin@ineos.ac.ru
bN. S. Enikolopov Institute of Synthetic Polymeric Materials, Russian Academy of Sciences,
70 ul. Profsoyuznaya, 117393 Moscow, Russian Federation.
A reaction of acetylacetone with the framework sandwichꢀtype metallosiloxanes (MOS) of
general formula [PhSiO2]6M6[PhSiO2]6, where M = Cu, Ni, Mn, was studied by GPC, 1H and
29Si NMR spectroscopy, Xꢀray diffraction, elemental and functional analysis. The reaction
involved replacement of the metal atoms with the hydrogen atoms and is accompanied by
the formation of the corresponding chelate complexes M(acac)2. Displacement of the metal
from the framework MOS leads to the destruction of molecular skeleton and formation of
phenylsiloxanes containing Si—OH groups. The yield and composition of the reaction products
considerably depend on the nature of the metal in [PhSiO2]6M6[PhSiO2]6. A selective substituꢀ
tion of the metal leads to the stereoregular hexahydroxyhexaphenylcyclohexasiloxane,
[PhSiO(OH)]6, cisꢀisomer. The structure and composition of the crystalline hexahydrꢀ
oxyhexaphenylcyclohexasiloxane obtained were confirmed by 29Si NMR spectroscopy, Xꢀray
1
diffraction study, and functional analysis, while its TMS derivative was studied with H NMR
spectroscopy and GPC. Using a framework manganese phenylsiloxane as an example, a reversꢀ
ible character of the process has been established and an alternative synthesis of this compound
from hexahydroxyhexaphenylcyclohexasiloxane and Mn(acac)2 has been accomplished for the
first time.
Key words: framework copperꢀ, nickelꢀ, and manganeseꢀcontaining organometallosiloxanes,
3d metal complexes, destructive substitution of metals, reaction with βꢀdiketones, acetylacetoꢀ
nates, organometallic synthesis, stereoregular organo(hydroxy)cyclosiloxanes.
Lately, organometallosiloxanes (MOS) attract increasꢀ
ing interest due to their specific structure and reactivity.1—7
Unusal chemical properties of MOS are due to the
presence of differing (Si)O—Si and (Si)O—M bonds, the
former of which is susceptible to nucleophilic agents,
whereas the latter is easily destroyed upon the action of
electrophiles.
Upon preparation of MOS with trifunctional (orgaꢀ
nosilsesquioxane) structural units RSiO3/2, a mixture of
individual crystalline MOS with polymeric metallosiloxꢀ
anes is formed. In the case of individual MOS, the archiꢀ
tecture of metal complexes formed has a complex spatial
structure in the form of cellular threeꢀdimensional netꢀ
work, whose formation is determined by a decisive role of
coordination properties of the transition metal ions1,2
forming the metal clusters.
flanked by two cyclosiloxane ligands bound with the MII
ions by covalent and coordination metallosiloxane bonds.
A unique structural organization of the framework
MOS is responsible for the possibility of their application
as synthons for the organoelement synthesis,3 as well as
metalꢀcontaining precursors in the synthesis of new cataꢀ
lysts,4 preparation of metalloceramic materials,5 and for
development of metalꢀcontaining nanocomposites.6,7
When we started our work, information on the reactivꢀ
ity of MOS in the disintegration reactions based on the
cleavage of the metalꢀoxide (Si)O—M bonds was rather
limited and was basically on the reactions of MOS with
electrophilic reagents (acids, anhydrides, organochlorosiꢀ
lanes). It is known that the reactions of this type are very
characteristic of metallosilicates,8 which are the closest
inorganic analogs of MOS. These reactions were successꢀ
fully used not only for the study of the silicate structures by
destructive silylation with trimethylchlorosilane9 (the
Lentz method), but also for the development of conveꢀ
nient methods for obtaining organoꢀinorganic polymers
The most acquainted representatives of individual
frameworkꢀtype MOS containing 3d transition metals are
the sandwichꢀstructure metal complexes, in which metal
atoms are placed in the central plane as the [Mn] clusters
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1340—1346, July, 2010.
1066ꢀ5285/10/5907ꢀ1369 © 2010 Springer Science+Business Media, Inc.

1370
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 7, July, 2010
Sergienko et al.
Scheme 1
and polyorganosiloxane resins based on mineral raw maꢀ
terials.8 In the series of the framework MOS, this is the
destruction of SiO—M metalꢀoxide bonds which was used
for the preparation of stereoregular cyclosiloxanes of
different structures,6,10,11 including mesomorphous orꢀ
ganocyclosiloxane hydroxy derivatives of stereoregular
structure. For example, disintegration of the framework
metallophenylsiloxanes containing the 3d transition metꢀ
al atoms upon the action of acids (HCl, H2S) leads
to stereoregular cyclosiloxanols [PhSiO(OH)]n, where
n = 4, 6, and 12 (see Refs 6 and 10). Other types of transꢀ
formations of MOS involving metalꢀoxide bonds virtually
are not studied so far. For development of controlled methꢀ
ods for the synthesis based on MOS, chemical transforꢀ
mations observed in the reactions with complexation
agents are of special interest.
The present work is devoted to the study of reacꢀ
tions of the framework MOS of general formula
[PhSiO2]6M6[PhSiO2]6 (M = Cu, Ni, Mn) with βꢀdikeꢀ
tones, forming stable complexes almost with all the tranꢀ
sition and nontransition metals.12 Taking into account
that the very possibility of obtaining stereoregular cyclosilꢀ
oxanes is determined by the presence in the structure of
the framework MOS of polydentate cyclic ligands of strictꢀ
ly determined spatial structure,1,2,13 during study of the
reactions of MOS with βꢀdiketones it seemed interesting
to find synthetic scope of these reactions, in particular, to
establish whether the ligands retain their configuration
during destruction of the framework MOS.
1: M = Cu (a), Ni (b), Mn (c)
of Si—OH groups to ionꢀcatalytic dehydrocondensation
and, as a result, high susceptibility to the effects of ionic
impurities, the silanol derivatives obtained by traditional
methods are unstable and can undergo spontaneous polyꢀ
condensation to highꢀmolecularꢀweight products. This
is the reason why methods for the preparation of cycloꢀ
siloxanols of given structure by acidic decomposition
of MOS, especially upon the action of strong acids, have
significant limitations. To suppress polycondensation,
it is necessary to use low starting concentrations of MOS,
thoroughly controlled reaction conditions, which affect
the dehydrocondensation rate (the pH value, temperꢀ
ature, the ratio, order, and rate of addition of reagents,
and etc).
Therefore, the reaction of MOS with diketones, in prinꢀ
ciple, can be considered as an alternative method for obꢀ
taining siloxanols, including also cyclosiloxanols of the
general formula [RSiO(OH)]n. It is important that aliꢀ
phatic βꢀdiketones are very weak acids. It is known12 that
acetylacetone (one of the most acidic aliphatic diketones,
pKa = 8.95) is a considerable inferior in acidity even to
Results and Discussion
such weak acids as H2S (pKa = 7.2; pKa = 14) and H2CO3
2
(pKa = 6.4; pKa =10.3).141 In this connection, one can
2
The study was devoted to the reaction of the frameꢀ
work MOS containing the 3d transition metal atoms
with typical representative of βꢀdiketones, acetylacetone
(Hacac). The sandwichꢀtype metal complexes of general
formula [PhSiO2]6M6[PhSiO2]6, where M = Cu (1a),
Ni (1b), Mn (1c), have been chosen as the objects for the
study. These compounds have similar sandwichꢀtype strucꢀ
ture, which is based on two sixꢀmembered siloxane rings
with six metal atoms placed between them. The difference
is that in the nickel (1b) and manganese (1c) compounds
a chlorine anion is encapsulated inside the framework
with the counterion (Na+) being placed in the outer sphere
of the molecule.
expe1ct that the reaction products of MOS with βꢀdiꢀ
ketones, i.e., silanols, formed according to Scheme 1,
would be more stable even in the presence of considerꢀ
able excess of βꢀdiketone or at higher concentrations
of reagents as compared to the products of the MOS
cleavage by traditional methods, for example, by minerꢀ
al acids.
Composition and structure of the reaction products
1
were studied by GPC, H and 29Si NMR spectroscopy,
Xꢀray diffraction, as well as by elemental and functional
analysis (to determine amount of the silanol Si—OH
groups).15 In addition, Me3SiOꢀderivatives were used to
study composition of the reaction products, which can be
obtained by both destructive trimethylsilylation of the
starting MOS11,16 (Scheme 2) and protection of the
silanol groups in the reaction products upon the action of
trimethylchlorosilane (Scheme 3).
Applicability of the silylation method, developed earlier
for the protection of terminal Si—OH groups in the linear
polydimethylsiloxanes,17 for the analysis of oligomeric
polyol systems (siloxanols) was confirmed in the model
reaction of [PhSi(OH)O]6 (2) with trimethylchlorosilane,
Me3SiCl. This reaction resulted in the high yield (75%) of
The reaction of the framework MOS with Hacac is
generally described by Scheme 1.
Extraction of metal from the metallosiloxane frameꢀ
work of MOS with diketones can result in the appearance
of silanol Si—OH groups in the reaction products. Firstly,
the scheme given resembles cleavage of MOS with acꢀ
ids,6,10 also leading to the formation of silanol derivatives.
However, there are significant differences, too.
As it is known, decomposition of MOS with acids is
accompanied by the side processes.9 Due to the tendency

Reactions of 3dꢀorganometallosiloxanes
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 7, July, 2010
1371
Scheme 2
as a convenient preparative method for the preparation of
reactive polysiloxanols, which are of considerable interest.
It was interesting to test this suggestion using a nonꢀ
ordered MOS, i.e., polymeric copperphenylsiloxane of
the same composition, as an example. It turned out that in
the case of polymeric copperphenylsiloxane (PCPS),
{[PhSiO2]2Cu}n, under analogous conditions (the ratio
Cu : Hacac = 1 : 2), a complete cleavage of the SiO—Cu
bonds also occurs with quantitative extraction of copper
from PCPS as a chelate complex Cu(acac)2. The IR specꢀ
troscopic data of the reaction products (after separation
from a Cu(acac)2 precipitate and precipitation from the
solution) contain a certain amount of silanol groups, that
is indicated by a broad absorption band of the OH groups
with the absorption maximum at 3342 cm–1 (see Ref. 18).
However, attempted quantitative determination of the OH
groups content using Chugaev—Tserevitinov method
failed, apparently, due to the too low content of the silanol
groups in the reaction products.
M = Cu, Ni, Mn
Scheme 3
the corresponding TMSꢀderivative 3, whose silanol Si—OH
groups are completely substituted for Me3SiO groups.
The study of the reaction systems showed that both the
framework and polymeric MOS react with acetylacetone
under mild conditions (at 25 °C). The color of the reacꢀ
tion mixture changed right after addition of Hacac into
the suspension of the framework copperphenylsiloxane
(1a) in diethyl ether with the appearance of strong blue
color characteristic of the copper acetylacetonate comꢀ
plex. After separation of a Cu(acac)2 precipitate and subꢀ
sequent reprecipitation with hexane from the ethereal filꢀ
trate, a colorless product was isolated as needleꢀlike crysꢀ
tals, which were 1,3,5,7,9,11ꢀhexahydroxyꢀ1,3,5,7,9,11ꢀ
hexaphenylcyclohexasiloxane (2) (see Scheme 1).
It was found that when the ratio Cu : Hacac = 1 : 2,
the yield of compound 2 in this reaction is quantitative
(≥92%).
The more detailed studies of the reaction of PCPS with
Hacac using H NMR spectroscopy confirmed the presꢀ
1
ence of secondary processes of polycondensation involvꢀ
ing silanol Si—OH groups. In this connection, we accomꢀ
plished trimethylsilylation of three samples taken at difꢀ
ferent stages of the process: the starting PCPS (I), the
ethereal solution of the reaction products of PCPS with
Hacac directly after removal of a Cu(acac)2 precipitate
(II), and the products in the final step obtained after preꢀ
cipitation from the ethereal solution with hexane and evapꢀ
oration of the solvent (III).
Analysis of composition of the TMS derivatives obꢀ
tained (based on the ratio of the integral intensities of
the signals for the Ph and Me groups in the 1H NMR
spectra) shows that the content of the Me3SiO groups
gradually decreases going from sample I to II and espeꢀ
cially to sample III. The ratio PhSi : SiMe3 in samples I,
II, and III is 1 : 1.37, 1 : 0.91, and 1 : 0.39, respectively.
Results of the study of all the three samples of the trimethꢀ
ylsilyl derivatives by GPC serve as an additional evidence
in favor of secondary condensation. A comparison of gelꢀ
chromatograms shows a broadening of the peak of the
reaction product and shift of its maximum toward more
highꢀmolecularꢀweight region (Fig. 1). These data clearly
indicate a polycondensation evolution, which is accompaꢀ
nied by the increase in the molecular weight and polydisꢀ
persity of the oligomers formed. A probable reason of
different stability of silanols formed upon decomposiꢀ
tion of the framework and polymeric MOS with acetylꢀ
acetone consists in the presence in PCPS of ionogenic
impurities as terminal functional groups (presumably,
SiONa or SiOCuCl).
The structure and composition of compound 2 were
confirmed by independent methods: Xꢀray diffraction, 29Si
NMR spectroscopy, the elemental and functional analysis
data (on amount of silanol Si—OH groups). The elemenꢀ
tal analysis data and amount of the silanol groups corꢀ
respond to the composition of the elementary unit
[PhSi(OH)O]. The 29Si NMR spectrum exhibits one sigꢀ
nal at δ –70.59 related to the silicon atom of the fragment
[PhSi(OH)O] in the sixꢀmembered ring.10 Xꢀray study
confirms that the compound obtained is identical to the
known compound [PhSi(OH)O]6 (see Ref. 10).
1
After silylation of compound 2, the H NMR specꢀ
trum of TMSꢀderivative 3 exhibits signals for the protons
of the SiMe3 groups (a singlet at δ 0.11) and phenyl groups
(a multiplet in the region of δ 6.8—7.15) characteristic of
the sixꢀmembered ring. Gel chromatography shows that
the retained volumes of TMSꢀderivative 3 and standard
compound [PhSiO(OSiMe3)]6 (2) are the same.
The reaction of the framework nickelphenylsiloxane
(1b) with acetylacetone proceeds similarly, rather at lower
rate. Under analogous conditions (at the ratio Hacac : Ni =
= 2 : 1), appearance of color is observed immediately after
The obtained results indicate that the extraction of
metal from MOS with βꢀdiketones can in principle serve

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Russ.Chem.Bull., Int.Ed., Vol. 59, No. 7, July, 2010
Sergienko et al.
V/mV
Table 1. The yields of compound 2 in the reaction
of the framework MOS 1a—c with acetylacetone
a
depending on the ratio Hacac : M
Compound
Yield of 2 (%) for Hacac : M
2 : 1
4 : 1
8 : 1
1a
1b
1c
92
64
—**
—*
67
—**
—*
—*
8
* No experiment was performed.
** No compound 2 was detected.
1
1
1
2
2
2
3
4
4
4
5
5
5
6
6
6
7
8
8
8
9
10 11 12 t/min
V/mV
200
b
the character of the reaction described is retained (Table 1).
The data obtained indicate that the reaction of the
framework MOS with βꢀdiketones, probably, proceeds
through the stepꢀwise replacement of the ligand surroundꢀ
ing of the metal atoms in the structure of molecular
framework.
Manganesephenylsiloxane (1c) exhibits the lowest reꢀ
activity in the series of compounds studied. In this case,
the product of complete substitution of the metal 2 is
successfully isolated in the about 8% yield only at a fourꢀ
fold excess of acetylacetone (Hacac : Mn = 8 : 1).
To sum up, reactivity of the framework MOS decreasꢀ
es with the change in the nature of metal in the order
Cu ≥ Ni > Mn.
The results obtained agree on the qualitative level with
stability constants of the corresponding metal acetylacetꢀ
onates: the higher is the stability constant of the metal
acetylacetonate, the higher is the yield of compound 2
(Table 2). Though there are no literature data on the
stability constants of compounds 1a—c, the increase in
the yield of product 2 in the reactions (see Scheme 1)
with the increase in the content of acetylacetone in the
starting mixture can indicate a reversible character of the
process. To check a suggestion on a possibility of the reꢀ
verse reaction, we attempted to accomplish an alternative
synthesis of the framework MOS from hexasiloxanol 2
and metal acetylacetonates. As it was noted, the frameꢀ
work manganeseꢀ and nickelphenylsiloxanes have encapꢀ
sulated chlorine ion. We have chosen lithium chloride as
a source of this ion, since it possesses good solubility in
ethanol, in which the reaction was run.
3
7
9
10 11 12 t/min
V/mV
200
c
3
7
9
10 11 12 t/min
Fig. 1. Gelꢀchromatograms of the samples of PCPS trimethylꢀ
silyl derivative : I (a), II (b), and III (c).
addition of nickelphenylsiloxane into the suspension beꢀ
gins, which is due to the formation of a Ni(acac)2 chelate
complex. After extraction of ~2/3 of the total amount
of metal the reaction is retarded. The elemental analysis
data show that the soluble reaction products, in addition
to compound 2, contain at this stage also compounds
formed as a result of incomplete extraction of the Ni atꢀ
oms from the starting framework nickelsiloxane 1b. Nevꢀ
ertheless, the yield of compound 2 reaches 64% after the
reaction is completed. When the amount of Hacac inꢀ
creases (with respect to the ratio Hacac : Ni = 2 : 1), the
yield of compound 2 increases insignificantly, however,
Table 2. Stability constants12 of metal acetylacetꢀ
onates formed in the reaction of the framework
MOS 1a—c with acetylacetone
Complex
logK1
logK2
Cu(acac)2
Ni(acac)2
Mn(acac)2
11.85
9.70
8.15
10.74
8.15
6.87

Reactions of 3dꢀorganometallosiloxanes
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 7, July, 2010
1373
O(2)
O(4)
thesized according to the procedures described earlier,2,13 manꢀ
ganese acetylacetonate was synthesized according to the known
procedure.20
Si(2)
Si(3)
Mn(2A)
Mn(2)
C(1S)
Si(1)
O(1)
O(3)
Reaction of the framework copperphenylsiloxane (1a) with
acetylacetone (the ratio Cu : Hacac = 1 : 2). Acetylacetone
(1.89 g, 18.90 mmol) was added to copperphenylsiloxane (3.45 g,
1.43 mmol) in diethyl ether (50 mL) and the mixture was stirred
at room temperature for 40 min. A precipitate of copper acetyꢀ
lacetonate was filtered off, washed on the filter with diethyl ether
(30 mL), and dried at room temperature until the weight was
constant to obtain copper acetylacetonate (2.25 g, 100%).
Found (%): Cu, 24.2. C10H14O4Cu. Calculated (%): Cu, 24.3.
Si was not detected. Hexane (80 mL) was added to the filtrate,
white needleꢀlike crystals formed were filtered off and dried at
room temperature until the weight was constant to obtain comꢀ
pound 2 (2.20 g, 92%). Found (%): C, 51.97; H, 4.56; Si, 20.20;
OH, 13.1. C36H36O12Si6. Calculated (%): C, 52.15; H, 4.38;
Si, 20.32; OH, 12.3. 29Si NMR, δ: –70.59 (s, PhSiO(OH)).
Reaction of polycopperphenylsiloxane {[PhSiO2]2Cu}n with
acetylacetone (the ratio Cu : Hacac = 1 : 2). Acetylacetone
(1.58 g, 15.80 mmol) was added to polycopperphenylsiloxane
(3.00 g, 7.90 mmol) in diethyl ether (60 mL) and the mixture was
stirred at room temperature for 40 min. A blue precipitate was
filtered off to obtain copper acetylacetonate (1.95 g, 95%). The
filtrate was concentrated to 15 mL, followed by addition of hexꢀ
ane (70 mL), a precipitate of a polymer formed was dried in vacuo
at room temperature until the weight was constant to obtain
polyphenylsiloxane (1.88 g, 85.6%) as a viscous resin. Found (%):
C, 51.4; H, 4.7; Si, 18.9. C36H36O12Si6. Calculated (%): C, 52.15;
H, 4.38; Si, 20.32. The Si—OH groups were not detected by the
Chugaev—Tserevitinov method,15 the IR spectrum (a solution
in hexachlorobutadiene) exhibits a broad band with the maxiꢀ
Mn(1A)
C(2S)
C(8S)
O(5)
Mn(1)
O(1S)
Mn(3)
Li(1)
O(6)
Si(4)
C(7S)
Li(1´)
O(11)
Si(6)
Mn(3A)
Si(5)
O(4S)
O(8)
O(7)
O(12)
O(10)
O(9)
Fig. 2. Metallosiloxane framework of compound 1c according to
the Xꢀray diffraction data. Two positions of the disordered lithiꢀ
um atom and the solvate molecules of ethanol closest to them
are shown, the chlorine atom inside the complex is not shown.
In fact, the reaction of Mn(acac)2 with compound 2 in
the presence of LiCl leads to a crystalline product in 62%
yield, whose structure according to the Xꢀray diffraction
data is identical to the framework manganesephenylsilꢀ
oxane [PhSiO2]6Mn6[PhSiO2]6, described earlier.19 The
structure of metallosiloxane framework of manganeseꢀ
phenylsiloxane (1c) synthesized by us is shown in Fig. 2.
The molecule of 1c is placed on the second order axis and
the insideꢀcage chlorine atom occupies double particular
position. In contrast to the copper complexes studied earꢀ
lier, the lithium atom does not coordinate the oxygen atꢀ
oms of the siloxane rings, rather it is placed in the outer
sphere with respect to the metallosiloxane framework and
is bound with the solvate molecules of EtOH.
mum at 3342 cm–1
.
Reaction of the framework nickelphenylsiloxane (1b) with
acetylacetone. A. The ratio Ni : Hacac = 1 : 2. Acetylacetone
(0.94 g, 9.43 mmol) was added to nickelphenylsiloxane (1b)
(2.00 g, 0.79 mmol) in diethyl ether (30 mL) and the mixture was
stirred at room temperature for 50 min. A pistachioꢀgreen preꢀ
cipitate was filtered off, washed on the filter with diethyl ether
(10 mL) to obtain a precipitate (1.64 g), which was a mixture of
the starting nickelphenylsiloxane and nickel acetylacetonate. The
ethereal filtrate was concentrated to 10 mL, followed by addition
of benzene (20 mL). After several minutes, needleꢀlike crystals
began to form in the solution. The crystals were filtered off and
dried in air at room temperature until the weight was constant to
obtain compound 2 (0.89 g, 64%) as white crystals. Found (%):
C, 52.82; H, 4.88; Si, 19.06; OH, 12.5. The solvent from the
mother solution was removed to dryness, the residue was dried
in vacuo until the weight was constant to obtain polynickelpheꢀ
nylsiloxane (0.12 g, 7.8%) as a pale green polymeric product.
Found (%): Si, 17.27; Ni, 5.0.
B. The ratio Ni : Hacac = 1 : 4. Compound 2 (0.91 g, 67%)
was obtained as white crystals similarly to procedure A from
nickelphenylsiloxane (1b) (2.00 g, 0.79 mmol) and acetylacetone
(1.89 g, 18.87 mmol). Found (%): C, 52.35; H, 4.3; Si, 19.55;
OH, 12.5. A pistachioꢀgreen precipitate (1.67 g), a mixture of the
starting nickelphenylsiloxane and nickel acetylacetonate, was
formed and polynickelphenylsiloxane (0.13 g, 8.8%) was isolated
as a pale green polymeric product. Found (%): Si, 17.87; Ni, 1.15.
Reaction of the framework manganesephenylsiloxane (1c)
with acetylacetone (the ratio Mn : Hacac = 1 : 8). Acetylacetone
In conclusion, successful accomplishment of an alꢀ
ternative synthesis of manganesephenylsiloxane from
Mn(acac)2 and hexahydroxyhexaphenylcyclohexasiloxane
confirms reversible character of the reaction of the frameꢀ
work MOS with acetylacetone.
Experimental
1
H and 29Si NMR spectra were recorded on a Bruker AV 300
spectrometer (300 MHz) in CDCl3 using Me4Si as an internal
standard. Gel permeation chromatography was performed in
a chromatographic system consisting of a HPP 5001 high presꢀ
sure pump (Czech Republic), a RIDK 102 refractometric detecꢀ
tor (Czech Republic), and a JETSTREAM 2 PLUS thermostat
of columns (KNAUER, Germany). The thermostat temperature
was 40 °C ( 0.1 °C), tetrahydrofuran was an eluent, the flow
rate was 1.0 mL min–1, a 300×7.8ꢀmm column filled with the
Phenogel sorbent (Phenomenex, USA) with the particles size of
5 μm, and pores size of 500 Å. Recording and processing of the
data were performed using the Mul´tiKhrom 1.6 GPC (Ampeꢀ
sand, Russia) and UniChrom 4.7 (Belarus) programs. IR spectra
were recorded on a Specord Mꢀ82 spectrometer. Silanol groups
were determined using the Chugaev—Tserevitinov method.15
The starting polymeric copperphenylsiloxane and framework
copperꢀ, nickelꢀ, and manganesephenylsiloxanes were synꢀ

1374
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 7, July, 2010
Sergienko et al.
(3.50 g, 35.40 mmol) was added to the framework manganeseꢀ
phenylsiloxane (1.60 g, 0.74 mmol) in diethyl ether (30 mL), the
mixture was stirred at room temperature for 24 h and a precipiꢀ
tate was filtered off. The brown precipitate (1.5 g) was a mixture
of the starting manganesephenylsiloxane and manganese acetyꢀ
lacetonate. The filtrate was concentrated to 10 mL and diluted
with benzene (40 mL), followed by the formation of needleꢀlike
crystals in the solution. The crystals were filtered off, and the
filtrate was again diluted with benzene (50 mL). The crystalline
precipitate formed was combined with that isolated earlier and
dried in air until the weight was constant to obtain compound 2
(0.10 g, 8%) as white crystals. Found (%): C, 52.80; H, 4.86;
Si, 18.47.
Reaction of hexahydroxyhexaphenylcyclohexasiloxane (2) with
manganese acetylacetonate. A solution of LiCl in ethanol (5 mL,
1.44 mmol mL–1) was added to a solution of Mn(acac)2•2H2O
(1.40 g, 4.34 mmol) in anhydrous ethanol (30 mL), followed by
addition of a solution of compound 2 (1.20 g, 8.68 mmol) in
anhydrous ethanol (30 mL). The mixture was stirred at room
temperature for 24 h. A crystalline precipitate formed was filꢀ
tered off and dried in air until the weight was constant to obtain
the framework manganesephenylsiloxane (1c) (1.05 g, 62%) as
lightꢀbrown crystals. Found (%): Si, 14.10; Mn, 14.18; Cl, 2.30.
The ratio Si : Mn : Cl = 12.0 : 6.2 : 1.5. C72H60O24Mn6LiCl.
Calculated (%): Si, 16.70; Mn, 16.33; Cl, 1.76. The ratio
Si : Mn : Cl = 12 : 6 : 1.
diethyl ether (15 mL) was added to a mixture of trimethylchloroꢀ
silane (2.90 g, 26.70 mmol) and pyridine (2.43 g, 30.72 mmol).
The mixture was stirred for 30 min at room temperature, and
then was refluxed for 2 h. After cooling, DI water (20 mL) and
concentrated hydrochloric acid (0.5 mL) were added to the mixꢀ
ture obtained. The mixture was separated using a separatory funꢀ
nel. The aqueous phase was extracted with diethyl ether (15 mL).
The ethereal extracts were combined and washed with water
until the reaction for the chlorine ions was negative. The organic
layer was dried with anhydrous sodium sulfate. Concentration of
the ethereal solution yielded compound [PhSiO(OSi(Me)3)]6 (3)
(0.95 g). 1H NMR, δ: 0.11 (s, 9 H, SiMe3); 6.80—7,15 (m, 5 H,
Ph). According to the data of 1H NMR spectrum, the ratio of
integral intensities of the protons SiC6H5 : Si(CH3)3 = 5 : 9, acꢀ
cording to the calculated data, 5 : 9. The yield was 75%.
Xꢀray study of compound 1c obtained by alternative syntheꢀ
sis was performed on a SMART APEX II CCD diffractometer
(MoꢀKα radiation, graphite monochromator, ωꢀscanning). The
structure was solved by the direct method and refined by the
least squares method in anisotropic fullꢀmatrix approximation
on F2hkl. Analysis of differential Fourierꢀsyntheses of electron
density showed that almost all the phenyl groups and some solꢀ
vate molecules of ethanol are disordered, further refinement of
these fragments was performed using limitations set on the C—C
and O—C bond distances. The lithium atom is also disordered
over two positions with equal population. The hydrogen atoms
of the methyl, methylene, and phenyl groups are calculated geoꢀ
metrically. The hydrogen atoms of the hydroxy groups were not
found. The principal crystallografic data and parameters of reꢀ
finement are given in Table 3.
Trimethylsilylation of hexahydroxyhexaphenylcyclohexasilꢀ
oxane (2). A solution of compound 2 (0.85 g, 10.00 mmol) in
Table 3. Crystallografic data and parameters of refinement of
structure 1c
Atom coordinates, bond distances, and bond angles were
deposited with the Cambridge Structural Database.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 06ꢀ03ꢀ32347)
and the Federal Agency for Science and Innovations of
Russian Federation (Federal Purposed Program "Supply
of the Community Centers with Scientific Instruments for
the Complex Studies in the Field of Physics and Nanoꢀ
structure Technologies", contract No. 02.552.11.7035).
Parameter
Value
Molecular formula
Molecular weight
T/K
Crystal system
Space group
Z
C87H91.40ClLi2Mn6O34Si12
2507.59
100
Monoclinic
C2/c
4
a/Å
b/Å
c/Å
α/deg
β/deg
γ/deg
30.6166(17)
18.8431(10)
20.5336(12)
90.00
98.7780(10)
90.00
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Received July 2, 2008;
in revised form December 29, 2009