Heptanuclear Cage CuII-Silsesquioxanes: Synthesis, Structure and Catalytic Activity

Article abstract of DOI:10.1002/ejic.201701340

Two prismatic phenyl- (PhSiO_1.5)₁₄(CuO)₇ (1, 29 % yield) and methyl- (MeSiO_1.5)₁₄(CuO)₇ (2, 19 % yield) heptacoppersilsesquioxanes were obtained by the interaction of Cu,Na-based cage silse

Full text of DOI:10.1002/ejic.201701340

A Journal of
Accepted Article
Title: Heptanuclear Cage Cu(II)-Silsesquioxanes. Features of
Synthesis, Structure and Catalytic Activity
Authors: Alexey Bilyachenko, Mikhail Levitsky, Alexander Korlyukov,
Victor Khrustalev, Yan Zubavichus, Lidia Shul’pina, Elena
Shubina, Anna Vologzhanina, and Georgiy Shul’pin
This manuscript has been accepted after peer review and appears as an
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201701340
Link to VoR: http://dx.doi.org/10.1002/ejic.201701340

European Journal of Inorganic Chemistry
10.1002/ejic.201701340
FULL PAPER
DOI: 10.1002/ejic.201((will be filled in by the editorial staff))
Heptanuclear Cage Cu(II)-Silsesquioxanes. Features of Synthesis, Structure and
Catalytic Activity
[
a,b]
[a]
[a,c]
Alexey N. Bilyachenko,* Mikhail M. Levitsky, Alexander A. Korlyukov,
[b]
d]
[a]
[a]
Victor N. Khrustalev, Yan V. Zubavichus,[ Lidia S. Shul’pina, Elena S. Shubina,
a]
[e,f]
Anna V. Vologzhanina,[ and Georgiy B. Shul’pin*
Keywords: Alkanes / Metallasilsesquioxanes / Copper complexes / Catalysis / Oxidation / X-ray diffraction
Two prismatic phenyl- (PhSiO1.5
MeSiO1.5 14(CuO) (2, 19% yield) heptacoppersilsesquioxanes were
obtained via interaction of Cu,Na-based cage silsesquioxanes
12(CuO) ] (R = Ph, Me) with 4,4’-bipyridine and
)
14(CuO)
7
(1, 29% yield) and methyl-
.
(
)
7
[
(RSiO1.5
)
4 4
(NaO0.5)
pyrazine, respectively, acting as “silent witness” ligands. Unusual
molecular topologies of both compounds 1 and 2 becoming the very first
representatives of cage silsesquioxanes with seven metal ions in their
cores were established by X-ray diffraction study.
Complex 1 was found to be active precatalyst in oxidation of alkanes
and 1-phenylethanol to alkyl hydroperoxides and acetophenone,
respectively. Alkanes have been oxidized by hydrogen peroxide and the
alcohol has been oxidized by tert-butyl hydroperoxide.
_
___________
[
a]
Nesmeyanov Institute of Organoelement Compounds, Russian
Academy of Sciences, Vavilova str., 28, Moscow 119991, Russia,
http://www.mhlab.ru/
E-mail: bilyachenko@ineos.ac.ru,
[
b] Peoples‘ Friendship University of Russia (RUDN University),
Miklukho-Maklay Str., 6, 117198 Moscow, Russia
c] Pirogov Russian National Research Medical University,
Ostrovitianov str., 1, 117997 Moscow, Russia
d] National Research Center “Kurchatov Institute”, Akademika
Kurchatova pl., 1, 123182 Moscow, Russia
e] Semenov Institute of Chemical Physics, Russian Academy of
[
[
[
Science, ul. Kosygina, 4, Moscow 119991, Russia
E-mail: shulpin@chph.ras.ru
[
f]
Plekhanov Russian University of Economics, Stremyannyi
pereulok, dom 36, Moscow 117997, Russia
Supporting information for this article is available on the WWW
under http://www.eurjic.org/
1
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European Journal of Inorganic Chemistry
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Introduction
Specific representatives of cage metallacomplexes, namely cage-like metallasilsesquioxanes, CLMSs, [1-5], are being intensely
studied as (pre)catalysts for numerous chemical processes of high relevance [6-11]. Among those, cage metallasilsesquioxanes
were found to be active in alkene polymerization [13-16], epoxidation [17-20] or epoxide ring opening [21], metathesis [22],
hydroformylation [23], Ullmann-Goldberg condensation [24] as well as amidation [25-28]. Recently, significant attention was
drawn to the potential of CLMS application in homogeneous oxidation of C-H compounds with an activity actually confirmed
for Fe- [26-27], Cr-[29], Ni-[30], and Co-based [31] compounds. In turn, the best potential for this type of catalytic activity was
found for Cu(II)-based cage silsesquioxanes. These complexes were found to be especially sensitive to conditions of synthesis.
This allowed us to isolate products of different nuclearity from 2 to 9 [5, 25, 32-33] and molecular topology. Sometimes
molecular topology and core nuclearity is governed by a promotive action of additional organic (P- [28] or N-based [34-37])
ligands or solvent molecules intentionally introduced into the reaction medium. But still general regularities underlying the self-
assembly processes in this extremely complex system remain elusive despite the fact that the total number of different CLMS
structure types rapidly increases. Thus more systematic studies are urgently needed. Logically, such a structural diversity brings
an opportunity to tailor conditions of catalytic reactions as well. Currently, an activity of cage coppersilsesquioxanes towards
peroxide assisted oxidation of different substrates, (i) arenes, (ii) alcohols and (iii) alkanes is established in a series of our works.
2 4
The most intriguing results were shown in the case of Cu and Cu -compounds [38]. Those pointed to a significant influence of
bulky silsesquioxane ligands on the activity of copper centers, similar to activity principle of multinuclear copper-containing
enzymes. Thus, we were interested in a further study of cage-like Cu-silsesquioxane synthesis and tests in oxidative catalysis. In
the recent time, some of us have shown the approach to the directed surpamolecular assembling of bi- and trimetallic cage Cu-
based silsesquioxanes, resulting in the organization of coordination polymers of different dimensionality [39]. The suggested
approach implies selection of appropriate bridges connecting neighbouring cages (solvates and alkali metal ions). In turn,
numerous coordination polymer structures were successfully synthesized with the use of rod-like linear N,N spacers [40]. Being
interested in the application of this synthetic tactic towards the design of metallasilsesquioxane coordination polymers, we have
performed experiments on the interaction of “globular” Cu,Na-silsesquioxanes with 4,4’-bipyridine and pyrazine. To our
surprise, both experiments failed in the sense of coordination polymer formation but gave rise to a structural rearrangement
affording the very first examples of heptanuclear cage Cu(II)-silsesquioxanes. We also present here application of the
heptacopper cage silsesquioxane in oxidative catalysis for the first time.
2
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European Journal of Inorganic Chemistry
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Results and Discussion
Synthesis and crystal structure
Two types of “globular” Cu,Na-silsesquioxanes (bearing phenyl [33, 41-42] (Figure 1, left) or methyl [43] (Figure 1, right)
substituents at silicon atoms) were chosen as a starting material for the interaction with rod-like N,N spacers due to the
convenient location of external (sodium) metal ions at equivalent positions. It gave us a reason to expect a possible formation of
1
D or 2D coordination polymer structure depending on the ratio “cage/spacer”.
4 4
Figure 1. Molecular structures of phenyl (left) and methyl (right) Cu ,Na -silsesquioxane of globular fashion
In realilty, while performing the interactions between globular Cu,Na-silsesquioxanes and N,N-rods (4,4’-bipyridine and
pyrazine), we have not observed formation of target coordination polymers. Instead, an unexpected assembly of high-nuclearity
prismatic copper silsesquioxanes were registered (Scheme 1, Figures 2, 1S).
Scheme 1. Simplified scheme of synthesis of
1 and 2.
3
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European Journal of Inorganic Chemistry
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Figure 2. Molecular structures of
1 (left) and 2 (right). Color code: Si – yellow, O – red, Cu – green, N – blue.
Such an unusual type of reactivity could be expressed as “silent witness”-type of activity from the viewpoint of used N,N-ligands.
Despite the failure in the synthesis of coordination polymer products, this unusual type of shape and nuclearity (Cu ) for the
resultant compounds points at the specific assistance of both 4,4’-bipyridine and pyrazine in the assembling of the products.
7
1-2
Symptomatically that only specific amine worked in each case and they are not exchangeable. This points to complicated
character of such unusual type of cage assembly with the significant role of steric effects of organic groups at silicon atoms (Me
vs Ph). Our team would try to shed some light on this process in the future reports. The second intriguing feature of both reactions
from Scheme 1 is a total elimination of sodium ions from the silsesquioxane matrix. To our best knowledge, such a
rearrangement procedure has been described in the literature only for the interaction of sodium-containing cage
metallasilsesquioxane with 2,2’-bipyridine [44].
Structurally, compounds
two tetradecamembered siloxane cycles coordinating the central copper oxide layer. The only observation of tetradecamembered
siloxane ligands involved in the formation of metallasilsesquioxane cage has been reported by some of us very recently for a Ni
based compound [45]. In turn, to the best of our knowledge, compounds and became the first representatives of heptanuclear
1 and 2 are similar to each other. The general feature is a prismatic (drum-like) molecular geometry with
2
-
1
2
cage silsesquioxanes. The main features of their molecular geometry are given in the Table S1 (ESI).
Topological studies of 1 and 2
In general, heptanuclear oxo-copper clusters are known to appear as disk-shaped units in adenine/hydroxide [46-48],
tartrate/hydroxide [49], 7-azaindole/hydroxide [50] or Schiff-base [51] mixtures. These complexes exhibit ferro-[48-49], ferri-
[
46] and antiferromagnetic [47, 50-51] behaviour. At the same time, previously reported complexes significantly differ from
compounds and in the mutual disposition and connectivity of metal atoms and bridging groups. Metal-containing clusters are
1
2
visualized in Fig. 3 and their connectivities are estimated within the NDk-m notation [52], where N is coordination number of
topologically non-equivalent nodes, D denotes a cluster periodicity (M for discrete clusters), k is the total number of metal atoms
in the cluster, and m is a classification number to distinguish topologically distinct clusters with equal NDk parameters. Within
this notation heptanuclear copper clusters in CLMSs realise the 2M7-1 topology, while all previously reported compounds belong
to the family of heptanuclear clusters with the 3,6M7-1 topology.
4
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European Journal of Inorganic Chemistry
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Figure 3. Top. The heptanuclear metal-containing clusters in CLMSs
1
and
2
(left) and in previously reported complexes (right)
connected by bridge oxygen atoms. Bottom. The graphs of corresponding clusters connectivity.
Catalytic studies
Compound 1 available in a higher yield as compared to 2 (29% vs 19%) was chosen for the first tests of heptanuclear cage silsesquioxane in
catalysis. Complex 1 was found to be an active precatalyst in the oxidation of cyclohexane with hydrogen peroxide. Fig. 4 shows the course
of cyclohexanol and cyclohexanone accumulation in the case when the reaction solution was not preliminarily reduced with PPh
and after such a treatment with PPh (Graph B). Earlier Shul’pin demonstrated that alkanes can be oxidized in acetonitrile solutions to
corresponding alkyl hydroperoxides by hydrogen peroxide in air in the presence of catalytic amounts of certain complexes. The alkyl
hydroperoxide is relatively stable in the solution, and can be easily reduced by PPh to corresponding alcohols. Chromatogram obtained
after reduction with PPh3 differs from the chromatogram obtained for the respective unreduced sample (compare graphs A and B in Figure
), which indicates that cyclohexyl hydroperoxide is formed in this reaction [53-61]. Hydrogen peroxide under the action of complex 1 is
3
(Graph A)
3
3
4
decomposed to generate very active hydroxyl radicals. The interaction of these radicals with the alkane molecules leads to the formation of
alkyl radicals which rapidly react with molecular atmospheric oxygen. Alkyl hydroperoxyl radicals are transformed further into the
corresponding alkyl hydroperoxide ROOH (Scheme 2):
H O
2
2
Alk(-H)=O
+ Alk-OH
e 
Alk-O-OH
(+1)
O2
Alk-H + HO .
H O
Alk .
Alk-O-O .
Ph3P
2
Ph P=O
3
Alk-OH
Scheme 2. The mechanism of oxidation reaction, involving formation of alkyl hydroperoxyl radicals
5
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European Journal of Inorganic Chemistry
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concentration (M)
B
0
0
0
.12
cyclohexanol
.08
after PPh3
.04
cyclohexanone
0
concentration (M)
cyclohexanol
A
0
.02
.01
before PPh3
0
cyclohexanone
0
0
1
2
time (h)
2 2
O
(50%, 3 M) catalyzed by complex 1 (5 × 10‒4 M) at 60 °C. Concentrations of
Figure 4. Oxidation of cyclohexane (0.23 M) with H
cyclohexanol and cyclohexanone were measured both before and after reduction with PPh
3
.
It should be noted that the oxidation requires the presence of nitric acid. Under conditions of the experiment shown in Fig. 4
the yield of oxygenates was 39%. This is a high value taking into account the pronounced inertness of alkanes. Usually in metal-
catalyzed alkane oxidation with hydrogen peroxides, yields of products do not exceed 10-20%.The oxidation of n-heptane
allowed us to measure the regioselectivity parameters for positions 1, 2, 3 and 4 : C(1):C(2):C(3):C(4) = 1.0:6.0:6.0:5.5. Reaction
proceeds non-selectively: the oxidation of cis-1,2-dimethylcyclohexane (Scheme 3) catalyzed by compound
1 gave the trans/cis-
products ratio of 0.7 (parameter trans/cis is the ratio of isomers of tert-alcohols with mutual trans- and cis-orientation of the
substituents in cyclohexane ring formed in the oxidation of cis- and trans-disubstituted cyclohexane). This data also indicates that
the reaction proceeds with the participation of free hydroxyl radicals generated from hydrogen peroxide. Compound
1 catalyzes
also the transformation of 1-phenylethanol into acetophenone under the action of tert-butyl hydroperoxide. Kinetics of the
reaction is shown in Fig. 5.
Scheme 3. The oxidation of cis-1,2-dimethylcyclohexane, catalyzed by complex 1
6
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European Journal of Inorganic Chemistry
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concentration (M)
0
0
0
.3
.2
.1
0
COCH3
0
4
8
12
16
time (h)
Figure 5. Formation of acetophenone in the oxidation of 1-phenylethanol (0.33 M) with TBHP (70% aqueous, 1.2 M) catalyzed by complex
‒
4
1
(5 × 10 M) at 50 °C.
Conclusions
7 7
The very first examples of heptanuclear cage silsesquioxanes, (PhSiO1.5)14(CuO) 1 and (MeSiO1.5)14(CuO) 2, were obtained as a
result of structural rearrangement of globular Cu,Na-based cage silsesquioxanes in the presence of rod-like N,N ligands (4,4’-
bipyridine and pyrazine, respectively). The role of these ligands, despite their absence in the composition of products and , is
nevertheless evident and may be regarded as an “assistant” or “silent witness” one. In our future reports, we will try to shed light
onto principles of the cage metallasilsesquioxanes’ self-assembly in the presence of additional agents. Complex was found to be
1
2
1
an active precatalyst in the oxidation of alkanes and 1-phenylethanol to alkyl hydroperoxides and acetophenone, respectively.
EXPERIMENTAL SECTION
Synthesis.
MeSi(OMe)
atmosphere.
3
, solvents and N-ligands were purchased from Acros Organics and used as received. All manipulations required no inert
Complex 1
1
(
g (0.387 mmol) of (Ph12Si12Cu
equipped with condenser and magnetic stirrer) and dissolved in 50 ml of DMF. After complete dissolution, 0.1 g (0.77 mmol) of anhydrous
CuCl was added at once. Reaction mixture was heated at reflux for 2 hours, then filtered hot from the insoluble fraction. To resulted
4 4 8
Na O24)(BuOH) (obtained by the method described in ref. 33) were placed in a round-bottom flask
2
filtrate, 0.06 g (0.4 mmol) of 4,4’-bipyridine were added. Solution was left under stirring overnight, then layered by 5 ml of hexane and left
for crystallization. After two weeks the formation of a crystalline phase (0.30 g, 29% yield) was observed. Crystals were used for single
crystal X-ray diffraction analysis (see below for details). Dried crystalline material was used for XRF analysis (spectrometer VRA-30).
7
Elemental analysis calcd. (%) for C84H70Cu O28Si14 Cu 18.80, Si 16.62, N 0; found Cu 18.67, Si 16.47, N 0.
Complex 2
1
g (7.34 mmol) of MeSi(OMe)
3
was placed in a round-bottom flask (equipped with condenser and magnetic stirrer) and dissolved in 50 ml
EtOH. Afterwards, 0.29 g (7.34 mmol) of solid NaOH was added and the mixture was heated at reflux for 2.5 hours. Then, 0.33 g (2.44
mmol) of anhydrous CuCl
2
was added at once, reaction mixture was left stirring overnight and then filtered from NaCl. The filtrate gave
7
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European Journal of Inorganic Chemistry
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crystalline material (0.71 g, 72% yield) appropriate for X-ray diffraction study in one week (complex 2a, (Me12Si12Cu
below and ESI for details). Dried crystalline material was used for XRF analysis (spectrometer VRA-30). Elemental analysis calcd. (%) for
Na 24Si12 Cu 20.37, Si 27.01, Na 7.37; found Cu 20.11, Si 26.89, Na 7.30.
4 4 8
Na O24)(EtOH) , see
C
12
H
36Cu
4
4
O
0
.4 g (0.248 mmol) of complex 2a, (Me12Si12Cu
magnetic stirrer) and dissolved in 50 ml of mixture (1:1) MeOH/DMSO. After complete dissolution, 0.065 g (0.483 mmol) of anhydrous
CuCl was added at once. Reaction mixture was heated at reflux for 2 hours, then filtered hot from the insoluble fraction. To resulted
4 4 8
Na O24)(EtOH) , was placed in a round-bottom flask (equipped with condenser and
2
filtrate, 0.02 g (0.250 mmol) of pyrazine was added. Solution was left under stirring overnight, then layered by 5 ml of hexane and left for
crystallization. After two weeks the formation of a crystalline phase (0.075 g, 19% yield) was observed. Crystals were used for single
crystal X-ray diffraction analysis (see below for details). Dried crystalline material was used for XRF analysis (spectrometer VRA-30).
7
Elemental analysis calcd. (%) for C14H42Cu O28Si14 Cu 29.72, Si 26.27, N 0; found Cu 29.61, Si 26.19, N 0.
X-ray studies
X-ray diffraction data for 1 were collected with Bruker APEX II CCD diffractometer using graphite monochromated Mo Kα radiation in
Center for molecular composition studies of INEOS RAS. X-ray diffraction data for 2 and 2a were collected at the ‘Belok’ beamline [62]
(λ = 0.96990 Å) of the Kurchatov Synchrotron Radiation Source. In total, 480-720 frames were collected with an oscillation range of 1.0 in
the φ-scanning mode using two different orientations for each crystal. The data were indexed and integrated using the utility iMOSFLM
from the CCP4 software suite [63]. The semi-empirical correction for absorption was applied using the Scala program [64]. The structures
2
were solved by intrinsic phasing modification of direct methods and refined by a full-matrix least squares technique on F using SHELXL-
2
014 [65] and OLEX2 [66] software. Non-hydrogen atoms were found on difference Fourier maps and refined with anisotropic
displacement parameters with an exception for disordered carbon and oxygen atoms in 1. The positions of hydrogen atoms were calculated
and included in refinement in isotropic approximation by the riding model with the Uiso(H) = 1.5Ueq(C ) for methyl groups and 1.2Ueq(Cii
i
)
for other atoms, where Ueq(C) are equivalent thermal parameters of parent atoms. Details of data collection and refinement are listed in
Table S1. Molecular views of investigated compounds are given below (Figure S1).
CCDC numbers: 1585379 (1)
1517977 (2)
1585272 (2a)
Oxidation of alkanes
Catalyst 1 was introduced into the reaction mixture in the form of solid powder. The alkane was then added and the reaction started when
hydrogen peroxide was introduced in one portion. (CAUTION. The combination of air or molecular oxygen and H2O2 with organic
compounds at elevated temperatures may be explosive!). The reactions after addition of nitromethane as a standard compound were
analyzed by GC. As we made previously, the samples obtained in the alkane oxidation were typically analyzed twice (before and after their
treatment with PPh
AW-HMDS; carrier gas argon). This method (the comparison of chromatograms of the same sample obtained before and after addition of
PPh ) which was proposed by one of us earlier [53-61] allows us to estimate real concentration of alkyl hydroperoxide, ketone (aldehyde)
3
) by GC (the chromatograph LKhM-80-6 instrument, columns 2 m with 5% Carbowax 1500 on 0.25–0.315 mm Inerton
3
and alcohol present in the reaction solution. Attribution of peaks was made by comparison with chromatograms of authentic samples and by
GC–MS.
Oxidation of 1-phenylethanol
Catalyst 1 was used in the form of its stock acetonitrile solution. Aliquots of this solution were added to reaction mixtures. The reactions
were typically carried out in air atmosphere in thermostated Pyrex cylindrical vessels with vigorous stirring; total volume of the reaction
solution was 5 mL. (CAUTION: the combination of air or molecular oxygen and tert-butyl hydroperoxide with organic compounds at
elevated temperatures may be explosive!) Samples of the reaction mixture were taken after certain time intervals, and concentrations of
products (see Fig. 5) were measured using 1H NMR method (acetone-d
a standard; “Bruker AMX-400” instrument, 400 MHz).
6
was used as a component of the solvent and 1,4-dinitrobenzene as
Supporting Information (see footnote on the first page of this article): crystallographic details and cif files. This information is available free of charge via
the Internet at http://pubs.acs.org.
8
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European Journal of Inorganic Chemistry
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Acknowledgments
The publication was prepared with the support of the “RUDN University Program 5-100” and funded by RFBR according to the research projects (16-03-
0254 and 17-03-00993). Synchrotron single-crystal diffraction measurements were performed at the unique scientific facility Kurchatov Synchrotron
0
Radiation Source supported by the Ministry of Education and Science of the Russian Federation (project code RFMEFI61917X0007). GBS acknowledges
Plekhanov Russian University of Economics for support.
_
___________
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For table of contents
7 7
Heptanuclear Cu(II)-Silsesquioxanes: First examples of heptacoppersilsesquioxanes (PhSiO1.5)14(CuO) (1) and (MeSiO1.5)14(CuO) (2) were obtained via
interaction of Cu,Na-based cage silsesquioxanes with 4,4’-bipyridine and pyrazine, respectively, acting as “silent witness” ligands. Complex 1 was found to
be active precatalyst in oxidation of alkanes and 1-phenylethanol to alkyl hydroperoxides and acetophenone, respectively.
1
1
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