Si10Cu6N4 Cage Hexacoppersilsesquioxanes Containing N Ligands: Synthesis, Structure, and High Catalytic Activity in Peroxide Oxidations

Article abstract of DOI:10.1021/acs.inorgchem.7b02320

The synthesis, composition, and catalytic properties of a new family of hexanuclear Cu(II)-based phenylsilsesquioxanes are described here. Structural studies of 17 synthesized compounds revealed the general principle underlying their molecular topology: viz., a central metal oxide layer consisting of two Cu₃ trimers is coordinated by two cyclic [PhSiO_1.5]₅ siloxanolate ligands to form a skewed sandwich architecture with the composition [(PhSiO_1.5)₁₀(CuO)₆]²⁺. In addition to this O ligation by the siloxanolate rings, two opposite copper ions are additionally coordinated by the nitrogen atoms of corresponding N ligand(s), such as 2,2′-bipyridine (compounds 1-9), 1,10-phenanthroline (compounds 10-13), mixed 1,10-phenanthroline/2,2′-bipyridine (compound 14), or bathophenanthroline (compounds 15-17). Finally, the charge balance is maintained by two HO^- (compounds 1-7, 10-13, and 15-17), two H₃CO^- (compound 8), or two CH₃COO^- (compounds 9 and 14) anions. Complexes 1 and 10 exhibited a high activity in the oxidative amidation oxidation of alcohols. Compounds 1, 10, and 15 are very efficient homogeneous catalysts in the oxidation of alkanes and alcohols with peroxides.

Full text of DOI:10.1021/acs.inorgchem.7b02320

Article
pubs.acs.org/IC
Si Cu N Cage Hexacoppersilsesquioxanes Containing N Ligands:
10
6 4
Synthesis, Structure, and High Catalytic Activity in Peroxide
Oxidations
Alena N. Kulakova,†,‡ Alexey N. Bilyachenko,*
,†,‡
Mikhail M. Levitsky, Victor N. Khrustalev,
†
‡
†
,§
∥
∥
,⊥
Alexander A. Korlyukov, Yan V. Zubavichus, Pavel V. Dorovatovskii, Fred
́
er
́
ic Lamaty,*
Xavier Bantreil,⊥ Benoît Villemejeanne, Jean Martinez, Lidia S. Shul’pina, Elena S. Shubina,
⊥
⊥
†
†
†
#
†
†
Evgeniy I. Gutsul, Igor A. Mikhailov, Nikolay S. Ikonnikov, Ul’yana S. Tsareva,
,
#,∇
and Georgiy B. Shul’pin*
†
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Str., 28, Moscow, Russia
Peoples’ Friendship University of Russia (RUDN University), Miklukho-Maklay Str., 6, Moscow, Russia
Pirogov Russian National Research Medical University, Ostrovitianov str., 1, Moscow, Russia
‡
§
∥
National Research Center “Kurchatov Institute”, Akademika Kurchatova pl., 1, Moscow, Russia
⊥
Institut des Biomolec
Place Eugene Bataillon, 34095 Montpellier cedex 5, France
Plekhanov Russian University of Economics, Stremyannyi pereulok, dom 36, Moscow, Russia
́
ules Max Mousseron (IBMM), UMR 5247, CNRS, Universite
́
de Montpellier, ENSCM, Site Triolet,
̀
#
∇
Semenov Institute of Chemical Physics, Russian Academy of Sciences, ulitsa Kosygina, dom 4, Moscow, Russia
S Supporting Information
*
ABSTRACT: The synthesis, composition, and catalytic properties
of a new family of hexanuclear Cu(II)-based phenylsilsesquioxanes
are described here. Structural studies of 17 synthesized compounds
revealed the general principle underlying their molecular topology:
viz., a central metal oxide layer consisting of two Cu trimers is
3
coordinated by two cyclic [PhSiO ] siloxanolate ligands to
1
.5 5
form a skewed sandwich architecture with the composition
2
+
[
(PhSiO ) (CuO) ] . In addition to this O ligation by the
1.5 10 6
siloxanolate rings, two opposite copper ions are additionally coor-
dinated by the nitrogen atoms of corresponding N ligand(s),
such as 2,2′-bipyridine (compounds 1−9), 1,10-phenanthroline
(
(
compounds 10−13), mixed 1,10-phenanthroline/2,2′-bipyridine
compound 14), or bathophenanthroline (compounds 15−17).
−
−
Finally, the charge balance is maintained by two HO (compounds 1−7, 10−13, and 15−17), two H CO (compound 8), or
two CH COO (compounds 9 and 14) anions. Complexes 1 and 10 exhibited a high activity in the oxidative amidation
3
−
3
oxidation of alcohols. Compounds 1, 10, and 15 are very efficient homogeneous catalysts in the oxidation of alkanes and alcohols
with peroxides.
INTRODUCTION
metallasilsesquioxanes, CLMSs) has drawn special attention as
attractive molecular architectures exhibiting unusual magnetic
■
(
6
In the past decades, metal-containing cagelike compounds
polycyclic 3D structures with well-defined geometry) have
attracted enormous attention from scientific groups due to their
7
(
spin glass behavior) effects and opportunities for the creation
8
9
of inorganic materials or nanoparticles. In turn, great deal of
attention has been devoted to the investigation of the catalytic
activity of metallasilsesquioxanes. For example, their high activity
was reported for such reactions of high demand as olefin or ring-
opening polymerization, olefin epoxidation, polycarbonate
1
striking molecular topology as well as their huge potential for
10
2
practical applications. These latter applications include, for
11
3
example, intriguing cases of development of polymer science
12
13
4
and medicine. A diversity of self-assembly procedures was
14
15
5
synthesis, and a Meerwein−Ponndorf reaction, as well as for
hydroformylation. In turn, our team reported on the catalytic
elaborated for the construction of cagelike compounds, sug-
gesting different ideas on structure control by means of, e.g., an
appropriate choice of linkers or ligand shape.
16
5
b
5d
Among the variety of metal-containing cage complexes,
a family of RSiO1.5-based metallacomplexes (cagelike
Received: September 13, 2017
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.7b02320
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Inorganic Chemistry
Article
activity of cagelike metallasilsesquioxanes in oxidative hydro-
n-heptane, and dried under vacuum. Anal. Calcd for [(PhSiO1.5
)
10(CuO)
6
17
18
(
HO ) (C H N ) ]: Cu, 18.16; N, 2.67; Si, 13.38. Found (for
carbon functionalization and amidation reactions. Very
recently, some of us presented the first example of the successful
testing of CLMSs, including additional organic (phosphorus-
0.5 2 10 8 2 2
vacuum-dried sample): Cu, 18.07; N, 2.59; Si, 13.29. Yield: 0.36 g (61%).
Complex 2. A 1 g portion (5.04 mmol) of PhSi(OMe) , 0.20 g
3
1
9
(5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
were placed in a three-neck round-bottom flask (equipped with a
magnetic stirrer and condenser). The resulting solution was heated
under reflux for 1.5 h and then was cooled to room temperature, and
based ) ligands in such oxidative reactions. According to this, we
were interested in further investigation of “organic ligand
assisted” synthesis of metallasilsesquioxanes and the application
of potential products of such an approach in catalysis. It should
be emphasized that among publications describing synthetic
approaches to CLMSs one could find some examples of CLMS
formation in the presence of different organic ligands. Mostly,
these ligands were used in the reaction of metallasilsesquioxane
synthesis as reagents (being a part of a metal complex) and they
were inherited in the composition of the product. These cases
0
.226 g (1.68 mmol) of CuCl was added at once. The mixture was
2
stirred for 3 h and filtered from NaCl. The filtrate was dried under
vacuum, and then 0.131 g (0.839 mmol) of 2,2′-bipyridine in 35 mL of
MeCN was placed in the same evaporation flask. The resulting solution
was intensely stirred for 2.5 h with a magnetic stirrer and then filtered
from the insoluble precipitate. The filtrate was stored in a vial equipped
with a septum with a needle to allow the slow evaporation of solvents for
crystallization. After 1 week the formation of crystalline material was
observed; several single crystals were used for X-ray diffraction analysis
20
include the classical work on the very first cubane CLMS
complex with Cp*) synthesis as well as numerous types of other
23
(
(for details of the X-ray diffraction study see below). The rest of the
2
1
22
complexes: with carborane, acac, tricyclohexylphosphine,
cyclooctenyl, methyl, or silylamide ligands just to mention
a few. Several examples of postsynthesis CLMS functionalization
crystalline fraction was separated from the solution, washed with
2
4
25
26
n-heptane, and dried under vacuum. Anal. Calcd for [(PhSiO ) (CuO)
1
.5 10
6
(HO ) (C H N ) ]: Cu, 18.16; N, 2.67; Si, 13.38. Found (for
0.5
2
10
8
2 2
27
by the organic ligands N,N-dimethylhydroxylamine and acacH,
vacuum-dried sample): Cu, 18.05; N, 2.60; Si, 13.27. Yield: 0.24 g (40%).
28
29
Complex 3. A 1 g portion (5.04 mmol) of PhSi(OMe) , 0.20 g
5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
tris(2-pyridylmethyl)amine and bipy are also worth mention-
ing. Very recently, our group suggested a quite convenient
method of CLMS self-assembly, assisted by the interaction of
3
(
were placed in a three-neck round-bottom flask (equipped with
magnetic stirrer and condenser). The resulting solution was heated
under reflux for 1.5 h and then was cooled to room temperature, and
2
,2′-bipyridine or phenanthroline with the product of the inter-
30
action of methylalkoxysilane with NaOH and CuCl . It should
2
0.226 g (1.68 mmol) of CuCl was added at once. The mixture was
2
be mentioned that the nature of the silicon atom substituent
stirred for 3 h and filtered from NaCl. The filtrate was dried under
vacuum, and then 0.131 g (0.839 mmol) of 2,2′-bipyridine in 35 mL of a
MeCN/PhCN mixture (2/1) was placed in the same evaporation flask.
The resulting solution was intensely stirred for 2.5 h with a magnetic
stirrer and then filtered from the insoluble precipitate. The filtrate was
stored in a vial equipped with a septum with a needle to allow the slow
evaporation of solvents for crystallization. After 1 week the formation of
crystalline material was observed; several single crystals were used for
X-ray diffraction analysis (for details of the X-ray diffraction study see
below). The rest of the crystalline fraction was separated from the
solution, washed with n-heptane, and dried under vacuum. Anal. Calcd
for [(PhSiO ) (CuO) (HO ) (C H N ) ]: Cu, 18.16; N, 2.67; Si,
could have great influence on the process of cage assembly
7
b,d
18a,31
(
compare, for example, penta-
or hexanuclear
prismatic
32
CLMSs, characteristic for phenyl-substituted reagent, to octa-
3
0
or nonanuclear methyl-based prisms). This is why we were
interested in the investigation of self-assembling reactions involving
phenylalkoxysilane and different ligands of the 2,2′-bipy family.
These ligands (with a transfer from 2,2′-bipyridine to bath-
ophenanthroline) could give valuable information on the influence
of steric factors (due to an increase in N-ligand bulkiness) for the
process of cage product assembly. Of course, we were interested
in the first study of catalytic properties of potential products of
these reactions, CLMSs, bearing N ligands.
1.5 10
6
0.5
2
10
8
2 2
13.38. Found (for vacuum-dried sample): Cu, 18.07; N, 2.61; Si, 13.30.
Yield: 0.12 g (20%).
We present here an extended series of 17 complexes (with
Complex 4. A 1 g portion (5.04 mmol) of PhSi(OMe)
5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
3
, 0.20 g
(
2
,2′-bipy, phenanthroline, or bathophenanthroline ligands) and
were placed in a three-neck round-bottom flask (equipped with a
magnetic stirrer and condenser). The resulting solution was heated
under reflux for 1.5 h and then was cooled to room temperature, and
the determination of their structures by single-crystal X-ray
diffraction. A study of the catalytic activity of these complexes in
peroxide oxidations of alcohols and alkanes as well as in amidation
reactions under mild conditions is also described.
0
.226 g (1.68 mmol) of CuCl was added at once. The mixture was
2
stirred for 3 h and filtered from NaCl. The filtrate was dried under
vacuum, and then 0.131 g (0.839 mmol) of 2,2′-bipyridine in 35 mL of a
MeCN/PhCN mixture (1/2) was placed in the same evaporation flask.
The resulting solution was intensely stirred for 2.5 h with a magnetic
stirrer and then filtered from the insoluble precipitate. The filtrate was
stored in a vial equipped with a septum with a needle to allow the slow
evaporation of solvents for crystallization. After 1 week the formation of
crystalline material was observed; several single crystals were used for
X-ray diffraction analysis (for details of the X-ray diffraction study see
below). The rest of the crystalline fraction was separated from the
solution, washed with n-heptane, and dried under vacuum. Anal. Calcd
EXPERIMENTAL SECTION
■
Synthesis. PhSi(OMe) , solvents, and N ligands were purchased
3
from Acros Organics and used as received. All manipulations required
no inert atmosphere.
Complex 1. A 1 g portion (5.04 mmol) of PhSi(OMe) , 0.20 g
5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
3
(
were placed in a three-neck round-bottom flask (equipped with
magnetic stirrer and condenser). The resulting solution was heated
under reflux for 1.5 h and then was cooled to room temperature, and
0
.226 g (1.68 mmol) of CuCl was added at once. The mixture was
for [(PhSiO1.5)10(CuO) (HO0.5) (C10H N ) ]: Cu, 18.16; N, 2.67; Si,
6 2 8 2 2
2
stirred for 3 h and filtered from NaCl. The filtrate was dried under
vacuum, and then 0.131 g (0.839 mmol) of 2,2′-bipyridine in 35 mL of
DMSO was placed in the same evaporation flask. The resulting solution
was intensely stirred for 2.5 h with a magnetic stirrer and then filtered
from the insoluble precipitate. The filtrate was stored in a vial equipped
with a septum with a needle to allow the slow evaporation of solvents for
crystallization. After 1 week the formation of crystalline material was
observed; several single crystals were used for X-ray diffraction analysis
13.38. Found (for vacuum-dried sample): Cu, 18.09; N, 2.60; Si, 13.29.
Yield: 0.06 g (10%).
Complex 5. A 1 g portion (5.04 mmol) of PhSi(OMe) , 0.20 g
3
(5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
were placed in a three-neck round-bottom flask (equipped with a
magnetic stirrer and condenser). The resulting solution was heated
under reflux for 1.5 h and then was cooled to room temperature, and
0.226 g (1.68 mmol) of CuCl was added at once. The mixture was
2
(
for details of the X-ray diffraction study see below). The rest of the
stirred for 3 h and filtered from NaCl. The filtrate was dried under
vacuum, and then 0.131 g (0.839 mmol) of 2,2′-bipyridine in 35 mL of
crystalline fraction was separated from the solution, washed with
B
DOI: 10.1021/acs.inorgchem.7b02320
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
PhCN was placed in the same evaporation flask. The resulting solution
was intensely stirred for 2.5 h with a magnetic stirrer and then filtered
from the insoluble precipitate. The filtrate was stored in a vial equipped
with a septum with a needle to allow the slow evaporation of solvents for
crystallization. After 1 week the formation of crystalline material was
observed; several single crystals were used for X-ray diffraction analysis
were placed in a three-neck round-bottom flask (equipped with a
magnetic stirrer and condenser). The resulting solution was heated
under reflux for 1.5 h and then was cooled to room temperature,
and 0.226 g (1.68 mmol) of CuCl was added at once. The mixture
2
was stirred for 3 h and then mixed with 0.131 g (0.839 mmol) of
2,2′-bipyridine (solution in 35 mL of MeCN). The resulting solution
was intensely stirred for 2.5 h with a magnetic stirrer and then filtered
from the insoluble precipitate. The filtrate was stored in a vial equipped
with a septum with a needle to allow the slow evaporation of solvents for
crystallization. After 1 week the formation of crystalline material was
observed; several single crystals were used for X-ray diffraction analysis
(for details of the X-ray diffraction study see below). The rest of the
crystalline fraction was separated from the solution, washed with
n-heptane, and dried under vacuum. Anal. Calcd for [(PhSiO ) (CuO)
6
(
for details of the X-ray diffraction study see below). The rest of the
crystalline fraction was separated from the solution, washed with
n-heptane, and dried under vacuum. Anal. Calcd for [(PhSiO ) (CuO)
1.5 10
6
(
HO ) (C H N ) ]: Cu, 18.16; N, 2.67; Si, 13.38. Found (for
0.5 2 10 8 2 2
vacuum-dried sample): Cu, 18.07; N, 2.58; Si, 13.26. Yield: 0.08 g (14%).
Complex 6. A 1 g portion (5.04 mmol) of PhSi(OMe) , 0.20 g
5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
3
(
were placed in a three-neck round-bottom flask (equipped with magnetic
stirrer and condenser). The resulting solution was heated under reflux
for 1.5 h and then was cooled to room temperature, and 0.226 g
1
.5 10
(CH COO ) (C H N ) ]: Cu, 17.46; N, 2.57; Si, 12.86. Found (for
3
0.5
2
10
8
2 2
vacuum-dried sample): Cu, 17.37; N, 2.49; Si, 12.77. Yield: 0.15 g (25%).
(
1.68 mmol) of CuCl was added at once. The mixture was stirred for
Complex 10. A 1 g portion (5.04 mmol) of PhSi(OMe) , 0.20 g
2
3
3
h and filtered from NaCl. The filtrate was dried under vacuum, and
(5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
were placed in a three-neck round-bottom flask (equipped with a
magnetic stirrer and condenser). The resulting solution was heated
under reflux for 1.5 h and then was cooled to room temperature, and
then 0.131 g (0.839 mmol) of 2,2′-bipyridine in 35 mL of THF was
placed in the same evaporation flask. The resulting solution was
intensely stirred for 2.5 h with a magnetic stirrer and then filtered from
the insoluble precipitate. The filtrate was stored in a vial equipped with a
septum with a needle to allow the slow evaporation of solvents for
crystallization. After 1 week the formation of crystalline material was
observed; several single crystals were used for X-ray diffraction analysis
0.226 g (1.68 mmol) of CuCl was added at once. The mixture was
2
stirred for 3 h and filtered from NaCl. The filtrate was dried under
vacuum, and then 0.151 g (0.840 mmol) of 1,10-phenanthroline in
35 mL of DMSO was placed in the same evaporation flask. The resulting
solution was intensely stirred for 2.5 h with a magnetic stirrer and then
filtered from the insoluble precipitate. The filtrate was stored in a vial
equipped with a septum with a needle to allow the slow evaporation of
solvents for crystallization. After 1 week the formation of crystalline
material was observed; several single crystals were used for X-ray
diffraction analysis (for details of the X-ray diffraction study see below).
The rest of the crystalline fraction was separated from the solution,
washed with n-heptane, and dried under vacuum. Anal. Calcd for
[(PhSiO ) (CuO) (HO ) (C H N ) ]: Cu, 17.75; N, 2.61; Si,
(
for details of the X-ray diffraction study see below). The rest of the
crystalline fraction was separated from the solution, washed with
n-heptane, and dried under vacuum. Anal. Calcd for [(PhSiO ) (CuO)
1.5 10
6
(
HO ) (C H N ) ]: Cu, 18.16; N, 2.67; Si, 13.38. Found (for
0.5 2 10 8 2 2
vacuum-dried sample): Cu, 18.10; N, 2.59; Si, 13.29. Yield: 0.28 g (48%).
Complex 7. A 1 g portion (5.04 mmol) of PhSi(OMe) , 0.20 g
3
(
5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
were placed in a three-neck round-bottom flask (equipped with
magnetic stirrer and condenser). The resulting solution was heated
under reflux for 1.5 h and then was cooled to room temperature, and
1.5 10
6
0.5
2
12
8
2 2
13.08. Found (for vacuum-dried sample): Cu, 17.64; N, 2.53; Si, 12.99.
Yield: 0.39 g (65%).
0
.226 g (1.68 mmol) of CuCl was added at once. The mixture was
2
stirred for 3 h and filtered from NaCl. The filtrate was dried under
vacuum, and then 0.131 g (0.839 mmol) of 2,2′-bipyridine in 35 mL of a
toluene/DMSO mixture (3/1) was placed in the same evaporation flask.
The resulting solution was intensely stirred for 2.5 h with a magnetic
stirrer and then filtered from the insoluble precipitate. The filtrate was
stored in a vial equipped with a septum with a needle to allow the slow
evaporation of solvents for crystallization. After 1 week the formation of
crystalline material was observed; several single crystals were used for
X-ray diffraction analysis (for details of the X-ray diffraction study see
below). The rest of the crystalline fraction was separated from the
solution, washed with n-heptane, and dried under vacuum. Anal. Calcd
for [(PhSiO ) (CuO) (HO ) (C H N ) ]: Cu, 16.90; N, 3.73; Si,
Complex 11. A 1 g portion (5.04 mmol) of PhSi(OMe) , 0.20 g
3
(5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
were placed in a three-neck round-bottom flask (equipped with a
magnetic stirrer and condenser). The resulting solution was heated
under reflux for 1.5 h and then was cooled to room temperature, and
0.226 g (1.68 mmol) of CuCl was added at once. The mixture was
2
stirred for 3 h and filtered from NaCl. The filtrate was dried under
vacuum, and then 0.151 g (0.840 mmol) of 1,10-phenanthroline in
35 mL of toluene was placed in the same evaporation flask. The resulting
solution was intensely stirred for 2.5 h with a magnetic stirrer and then
filtered from the insoluble precipitate. The filtrate was stored in a vial
equipped with a septum with a needle to allow the slow evaporation of
solvents for crystallization. After 1 week the formation of crystalline
material was observed; several single crystals were used for X-ray
diffraction analysis (for details of the X-ray diffraction study see below).
The rest of the crystalline fraction was separated from the solution,
washed with n-heptane, and dried under vacuum. Anal. Calcd for
[(PhSiO ) (CuO) (HO ) (C H N ) ]: Cu, 17.75; N, 2.61; Si,
1.5 10
6
0.5
2
10
8
2 3
12.45. Found (for vacuum-dried sample): Cu, 16.81; N, 3.68; Si, 12.37.
Yield: 0.08 g (12%).
Complex 8. A 1 g portion (5.04 mmol) of PhSi(OMe) , 0.20 g
5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
3
(
were placed in a three-neck round-bottom flask (equipped with magnetic
stirrer and condenser). The resulting solution was heated under reflux
for 1.5 h and then was cooled to room temperature, and 0.226 g
1.5 10
6
0.5
2
12
8
2 2
13.08. Found (for vacuum-dried sample): Cu, 17.66; N, 2.54; Si, 12.99.
(
1.68 mmol) of CuCl was added at once. The mixture was stirred for 3 h
Yield: 0.22 g (37%).
2
and then mixed with 0.131 g (0.839 mmol) of 2,2′-bipyridine (solution
in 35 mL of THF). The resulting solution was intensely stirred for 2.5 h
with a magnetic stirrer and then filtered from the insoluble precipitate.
The filtrate was stored in a vial equipped with a septum with a needle to
allow the slow evaporation of solvents for crystallization. After 1 week
the formation of crystalline material was observed; several single crystals
were used for X-ray diffraction analysis (for details of the X-ray
diffraction study see below). The rest of the crystalline fraction was
separated from the solution, washed with n-heptane, and dried under
vacuum. Anal. Calcd for [(PhSiO ) (CuO) (CH O ) (C H N ) ]:
Complex 12. A 1 g portion (5.04 mmol) of PhSi(OMe) , 0.20 g
3
(5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
were placed in a three-neck round-bottom flask (equipped with a
magnetic stirrer and condenser). The resulting solution was heated
under reflux for 1.5 h and then was cooled to room temperature, and
0.226 g (1.68 mmol) of CuCl was added at once. The mixture was
2
stirred for 3 h and filtered from NaCl. The filtrate was dried under
vacuum, and then 0.151 g (0.840 mmol) of 1,10-phenanthroline in
35 mL of DMF was placed in the same evaporation flask. The resulting
solution was intensely stirred for 2.5 h with a magnetic stirrer and then
filtered from the insoluble precipitate. The filtrate was stored in a vial
equipped with a septum with a needle to allow the slow evaporation of
solvents for crystallization. After 1 week the formation of crystalline
material was observed; several single crystals were used for X-ray
1.5 10
6
3
0.5
2
10
8
2 2
Cu, 17.92; N, 2.63; Si, 13.20. Found (for vacuum-dried sample): Cu,
1
8.10; N, 2.59; Si, 13.29. Yield: 0.16 g (27%).
Complex 9. A 1 g portion (5.04 mmol) of PhSi(OMe) , 0.20 g
3
(
5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
C
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Inorganic Chemistry
Article
diffraction analysis (for details of the X-ray diffraction study see below).
The rest of the crystalline fraction was separated from the solution,
washed with n-heptane, and dried under vacuum. Anal. Calcd for
under reflux for 1.5 h and then was cooled to room temperature, and
0.226 g (1.68 mmol) of CuCl was added at once. The mixture was
2
stirred for 3 h and filtered from NaCl. The filtrate was dried under
vacuum, and then 0.280 g (0.840 mmol) of bathophenanthroline
(solution in 35 mL of toluene) was placed in the same evaporation flask.
The resulting solution was intensely stirred for 2.5 h with a magnetic
stirrer and then filtered from the insoluble precipitate. The filtrate was
stored in a vial equipped with a septum with a needle to allow the slow
evaporation of solvents for crystallization. After 1 week the formation
of crystalline material was observed; several single crystals were used for
X-ray diffraction analysis (for details of the X-ray diffraction study see
below). The rest of the crystalline fraction was separated from the
solution, washed with n-heptane, and dried under vacuum. Anal. Calcd
for [(PhSiO ) (CuO) (HO ) (C H N ) ]: Cu, 15.55; N, 2.28; Si,
[
1
(PhSiO ) (CuO) (HO ) (C H N ) ]: Cu, 17.75; N, 2.61; Si,
3.08. Found (for vacuum-dried sample): Cu, 17.68; N, 2.54; Si, 13.00.
1.5 10 6 0.5 2 12 8 2 2
Yield: 0.28 g (47%).
Complex 13. A 1 g portion (5.04 mmol) of PhSi(OMe) , 0.20 g
5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
3
(
were placed in a three-neck round-bottom flask (equipped with a
magnetic stirrer and condenser). The resulting solution was heated
under reflux for 1.5 h and then was cooled to room temperature ,and
0
.226 g (1.68 mmol) of CuCl was added at once. The mixture
2
was stirred for 3 h and then mixed with 0.151 g (0.840 mmol) of
,10-phenanthroline (solution in 35 mL of pyridine). The resulting
1
1.5 10
6
0.5
2
24 16
2 2
solution was intensely stirred for 2.5 h with a magnetic stirrer and then
filtered from the insoluble precipitate. The filtrate was stored in a vial
equipped with a septum with a needle to allow the slow evaporation of
solvents for crystallization. After 1 week the formation of crystalline
material was observed; several single crystals were used for X-ray
diffraction analysis (for details of the X-ray diffraction study see below).
The rest of the crystalline fraction was separated from the solution,
washed with n-heptane, and dried under vacuum. Anal. Calcd for
1
1.45. Found (for vacuum-dried sample): Cu, 15.47; N, 2.19; Si, 11.36.
Yield: 0.21 g (30%).
Complex 17. A 1 g portion (5.04 mmol) of PhSi(OMe) , 0.20 g
3
(5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
were placed in a three-neck round-bottom flask (equipped with a
magnetic stirrer and condenser). The resulting solution was heated
under reflux for 1.5 h and then was cooled to room temperature, and
0
.226 g (1.68 mmol) of CuCl was added at once. The mixture was
2
[
1
(PhSiO ) (CuO) (HO ) (C H N ) ]: Cu, 17.75; N, 2.61; Si,
3.08. Found (for vacuum-dried sample): Cu, 17.66; N, 2.52; Si, 12.99.
1.5 10 6 0.5 2 12 8 2 2
stirred for 3 h and then mixed with 0.280 g (0.840 mmol) of
bathophenanthroline (solution in 35 mL of benzene). The resulting
solution was intensely stirred for 2.5 h with a magnetic stirrer and then
filtered from the insoluble precipitate. The filtrate was stored in a vial
equipped with a septum with a needle to allow the slow evaporation of
solvents for crystallization. After 1 week the formation of crystalline
material was observed; several single crystals were used for X-ray
diffraction analysis (for details of the X-ray diffraction study see below).
The rest of the crystalline fraction was separated from the solution,
washed with n-heptane, and dried under vacuum. Anal. Calcd for
Yield: 0.18 g (31%).
Complex 14. A 1 g portion (5.04 mmol) of PhSi(OMe) , 0.20 g
5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
3
(
were placed in a three-neck round-bottom flask (equipped with a
magnetic stirrer and condenser). The resulting solution was heated
under reflux for 1.5 h and then was cooled to room temperature, and
0
.226 g (1.68 mmol) of CuCl was added at once. The mixture was
2
stirred for 3 h and filtered from NaCl. The filtrate was dried under
vacuum, and then 0.065 g (0.420 mmol) of 2,2′-bipyridine and 0.076 g
[(PhSiO ) (CuO) (HO ) (C H N ) ]: Cu, 15.55; N, 2.28; Si, 11.45.
1.5 10 6 0.5 2 24 16 2 2
(
0.420 mmol) of 1,10-phenanthroline (solution in 35 mL of DMF) was
Found (for vacuum-dried sample): Cu, 15.48; N, 2.18; Si, 11.34. Yield:
0
placed in the same evaporation flask. The resulting solution was
intensely stirred for 2.5 h with a magnetic stirrer and then filtered from
the insoluble precipitate. The filtrate was stored in a vial equipped with a
septum with a needle to allow the slow evaporation of solvents for
crystallization. After 1 week the formation of crystalline material was
observed; several single crystals were used for X-ray diffraction analysis
.15 g (22%).
IR spectra were recorded on a Shimadzu IR Prestige21 FTIR spectro-
meter in KBr pellets. UV−vis absorption spectra were recorded on a
Varian Cary 50 spectrophotometer in a cell with 10 mm optical path
length.
X-ray Crystal Structure Determination. X-ray diffraction data for
, 4, 6−9, 11, 12, 14, 16, and 17 were collected on the “Belok” beamline
(
for details of the X-ray diffraction study see below). The rest of the
1
crystalline fraction was separated from the solution, washed with
of the National Research Center “Kurchatov Institute” (Moscow,
Russian Federation) using a Rayonix SX165 CCD detector. A total of
7
mode and corrected for absorption using the Scala program. The data
were indexed, integrated, and scaled using the utility iMOSFLM in the
CCP4 program. X-ray diffraction data for 2, 3, 5, 10, 13, and 15 were
n-heptane, and dried under vacuum. Anal. Calcd for [(PhSiO ) (CuO)
1.5 10
6
(
CH COO ) (C H N )(C H N )]: Cu, 17.27; N, 2.54; Si, 12.72.
3 0.5 2 12 8 2 10 8 2
20 images were collected using an oscillation range of 1.0° and φ scan
Found (for vacuum-dried sample): Cu, 17.20; N, 2.47; Si, 12.67. Yield:
33a
0
.19 g (31%).
Complex 15. A 1 g portion (5.04 mmol) of PhSi(OMe) , 0.20 g
3
33b
(
5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
collected on a three-circle Bruker APEX-II CCD diffractometer
were placed in a three-neck round-bottom flask (equipped with a
magnetic stirrer and condenser). The resulting solution was heated
under reflux for 1.5 h and then was cooled to room temperature, and
(graphite monochromator, φ and ω scan mode) and corrected for
33c
absorption using the SADABS program. The data were indexed and
integrated using the SAINT program. For details, see Table S1 in the
Supporting Information. The structures were determined by direct
3
3d
0
.226 g (1.68 mmol) of CuCl was added at once. The mixture was
2
stirred for 3 h and filtered from NaCl. The filtrate was dried under
vacuum, and then 0.280 g (0.840 mmol) of bathophenanthroline
2
methods and refined by full-matrix least-squares techniques on F with
anisotropic displacement parameters for non-hydrogen atoms. In the
case of 7, 8, 10, 11, 16, and 17, all attempts to model and refine positions
of the solvate molecules were unsuccessful. Therefore, their contri-
bution to the total scattering pattern was removed by use of the utility
SQUEEZE in PLATON06 or the Solvent mask procedure in the
Olex2 program. The hydrogen atoms of the OH groups as well as the
water and acetonitrile solvate molecules were localized in the difference
Fourier map and included in the refinement within the riding model
with fixed isotropic displacement parameters. The other hydrogen
atoms were placed in calculated positions and refined within the riding
model with fixed isotropic displacement parameters (Uiso(H) = 1.5Ueq(C)
(
solution in 35 mL of MeCN) was placed in the same evaporation flask.
The resulting solution was intensely stirred for 2.5 h with a magnetic
stirrer and then filtered from the insoluble precipitate. The filtrate was
stored in a vial equipped with a septum with a needle to allow the slow
evaporation of solvents for crystallization. After 1 week the formation
of crystalline material was observed; several single crystals were used for
X-ray diffraction analysis (for details of the X-ray diffraction study see
below). The rest of the crystalline fraction was separated from the
solution, washed with n-heptane, and dried under vacuum. Anal. Calcd
for [(PhSiO ) (CuO) (HO ) (C H N ) ]: Cu, 15.55; N, 2.28; Si,
3
3e
1.5 10
6
0.5
2
24 16
2 2
11.45. Found (for vacuum-dried sample): Cu, 15.48; N, 2.20; Si, 11.36.
Yield: 0.28 g (41%).
for the CH
groups and 1.2Ueq(C) for the other groups). All calculations
3
33f 33g
Complex 16. A 1 g portion (5.04 mmol) of PhSi(OMe) , 0.20 g
were carried out using the SHELXTL and Olex2
programs.
3
(
5 mmol) of NaOH, and 20 mL of an ethanol/methanol (1/1) mixture
Crystallographic data for 1−17 have been deposited with the Cambridge
Crystallographic Data Center as files CCDC 1565028−1565032,
1565113−1565124.
were placed in a three-neck round-bottom flask (equipped with a
magnetic stirrer and condenser). The resulting solution was heated
D
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Figure 1. General scheme of synthesis of hexacoppersilsesquioxanes 1−9 containing 2,2′-bipyridine ligands. Color code: Si, yellow; O, red; C, black;
H, gray; Cu, green; N, blue.
sept = septuplet, m = multiplet; coupling constant in Hz; integration.
13
C NMR spectra were recorded on a Bruker Avance AM 100 MHz
spectrometer. Chemical shifts are reported in ppm and referenced to the
solvent peak (CDCl at 77.16 ppm).
3
General Procedure for the Formation of Amides. In a sealed tube
were added successively amine hydrochloride (0.5 mmol), CaCO3
(
50.1 mg, 0.5 mmol), CH CN (1 mL), 1 (20 μL of a solution of
3
1
.8 mg of 1 in 2 mL of CH Cl ) or 10 (40 μL of a solution of 1.7 mg of 10
2 2
in 4 mL of CHCl ), benzylic alcohol (105 μL, 1.0 mmol), and TBHP
3
(5.5 M in nonane, 225 μL, 1.25 mmol). The mixture was stirred at 80 °C
for 2 h, and TBHP (5.5 M in nonane, 225 μL, 1.25 mmol) was again
added to the mixture. After 16−22 h at 80 °C, the mixture was cooled to
room temperature and 1 N HCl and EtOAc were added. The mixture
was extracted twice with EtOAc, and the combined organic phases were
Figure 2. Presumable scheme of oxidation of a primary alcohol directly
to the corresponding carboxylic acid.
washed with a saturated solution of NaHCO and brine and concen-
3
trated under reduced pressure. To remove the excess of benzylic alcohol,
Oxidation of Alcohols to Amides. All reagents were purchased
from Aldrich Chemical Co., Fluka, and Alfa Aesar and used without
further purification. Analyses were performed at the “Plateforme
Technologique Laboratoire de Mesures Physiques” (IBMM, Universite
de Montpellier). H NMR spectra were recorded on a Bruker Avance
DPX 400 MHz spectrometer. Chemical shifts are reported in ppm and
8
0 mL of H O was added and evaporated under reduced pressure.
2
The crude product was then purified using silica gel chromatography
with gradients of cyclohexane/EtOAc to yield the pure compounds.
Oxidation of Alcohols to Ketones. The substrate was added to the
reaction solution, and the process was started when the oxidant was
introduced in one portion. The reactions of alcohols were carried out in
air in thermostated Pyrex cylindrical vessels with vigorous stirring and
́
1
referenced to the solvent peak (CDCl at 7.26 ppm). Data are reported
3
as follows: s = singlet, d = doublet, t = triplet, q = quadruplet, qt = quintuplet,
E
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using MeCN as solvent. Concentrations of products obtained in the
solution. Attribution of peaks was made by comparison with chromato-
grams of authentic samples and by GC-MS. In our kinetic studies
described below, we measured concentrations of cyclohexanone and
cyclohexanol only after reduction of the reaction mixture with PPh3
because in this case we measured the precise concentration of a sum of
the oxygenates. Blank experiments with cyclohexane showed that in the
absence of a catalyst products were formed in negligible concentrations.
oxidation of 1-phenylethanol after certain time intervals were measured
1
using H NMR methods (solutions in acetone-d ; Bruker AMX-400
6
instrument, 400 MHz). In the oxidation of cyclohexanol, concentrations
of the substrate and products were measured by GC.
Oxidation of Alkanes. Catalysts 1, 10, and 15 were introduced into
the reaction mixture in the form of solid powder. The alkane was then
added, and the reaction was started when hydrogen peroxide was
introduced in one portion. (Caution! The combination of air or
molecular oxygen and H O with organic compounds at elevated tem-
RESULTS AND DISCUSSION
■
2
2
peratures may be explosive!). The reactions after addition of nitro-
methane as a standard compound were analyzed by GC. As we had done
previously, the samples obtained in the alkane oxidation were typically
Synthesis and Structures of the Complexes. A two-stage
scheme of synthesis of complexes of Cu(II) phenylsilsesquiox-
anes with bidentate N ligands was applied. In the first step of the
reaction an interaction of the phenyltrialkoxysilane PhSi(OMe)3
with sodium hydroxide (NaOH) in alcohol solution occurs.
analyzed twice (before and after their treatment with PPh ) by GC
3
(
Model 3700 chromatograph; fused silica capillary column FFAP/
OV-101 20/80 w/w, 30 m × 0.2 μm × 0.3 μm; argon as a carrier gas).
This method (the comparison of chromatograms of the same sample
6a,f
According to previous results, this reaction leads to the forma-
tion of highly reactive sodium siloxanolate species. No doubt, an
investigation of such alkali-metal-based species is an interesting
obtained before and after addition of PPh ) which was proposed by
3
34
Shul’pin earlier allows us to estimate the real concentration of alkyl
35
hydroperoxide, ketone (aldehyde) and alcohol present in the reaction
scientific topic by itself. Nevertheless, in the context of cage
Figure 3. “Acetonitrile to copper” coordination in complex 9: (a) van der Waals radii given to show the steric limitations; (b) molecular structure of
complex 9. Color code: Si, yellow; O, red; C, dark gray; H, light gray; Cu, green; N, blue.
F
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Article
metallasilsesquioxane assembly, an elucidation of the sodium
siloxanolate structure in this work seemed for us to be not very
hexacopper complexes 1−9 (Figure 1). These products are
characterized by the presence of analogous central frameworks,
35a,m
35i,k,l,n,p,r
essential. In several works by us
and others
it has
with two cisoid silsesquioxane rings [(PhSiO1.5
skewed sandwich cage.
Symptomatically, each of the complexes 1−9 contains six Cu
) ] forming a
5
been established that such siloxanolates tend to form tri- or
tetrameric cyclic structures in the crystal phase. In turn, the
corresponding trimeric silsesquioxane cycles were never
observed in the composition of arised CLMSs, while tetrameric
2
+
ions, giving 12 positive charges. Two pentameric silsesquioxane
ligands donate 10 negative charges. Two extra negative charge
carriers are hydroxide, methoxide, and acetate anions (for 1−7, 8,
and 9, respectively). The formation of some of these anions
deserves to be discussed. The appearance of methoxy groups in 8
could be easily explained by the methanol-containing media of
synthesis. The formation of acetate groups in 9 is not so evident.
Similarly to copper methylsilsesquioxanes from ref 30, we could
suggest the possible mechanism of homogeneous oxidation of
ethanol (in the presence of copper ions), giving rise to the acetate
groups (Figure 2). This transformation could be compared to
6g
cycles remain an extremely rare type of CLMS ligand. Thus,
we focus on the second stage of the synthetic schemethe
in situ interaction of presumably formed sodium siloxanolate
[
(PhSiO )(NaO )] with CuCl inthepresenceof2,2′-bipyridine
1.5
0.5
n
2
in different solvent media. It was found that, despite changes in
the reaction regime, the synthesis gives rise to a family of only
3
6a
the process mentioned earlier by Rudakov and co-workers
36b
as well as Sakharov and Skibida: namely, the oxidations of
primary alcohols directly to the corresponding carboxylic acids in
aqueous alkaline solutions catalyzed by copper phenanthroline
complexes.
Another attractive feature of complex 9 in comparison to
−
−
compounds 1−8 is “a flipping” of charged (HO , CH COO ,
3
−
CH O ) and neutral (DMSO, MeCN, THF, PhCN, H O)
3
2
ligands. Namely, in the case of compounds 1−8 the “charge
−
−
balancing” groups (HO or CH O ) directly coordinate Cu(II)
3
ions (forming tight ion pairs). In case of compound 3 the
positions next to Cu(II) are occupied by neutral acetonitrile
−
molecules (Figure 3a). Anionic CH COO fragments are
3
located in the outer sphere of the complex, forming solvent-
separated ion pairs (Figure 3b). We may suggest as an explanation
of this fact the coordinative strength of acetonitrile (ligation
factor) acting along with the bulkiness of phenyl and acetate
groups (steric factor). For the methyl-basedhexacopper complexes
from ref 30 such “flipping” was not detected.
In turn, we would like to mention several features of products
5, 7, and 8 in the context of their solvate surroundings. The
presence of benzonitrile ligands in the composition of 5 allows us
Figure 4. Triple π−πaromatic stacking (phenyl group−bipy−benzonitrile)
interactions in complex 5. Color code: Si, yellow; O, red; C, gray; Cu, green;
N, blue.
Figure 5. General scheme of synthesis of hexacoppersilsesquioxanes 10-13 containing 1,10-phenanthroline ligands. Color code: Si, yellow; O, red;
H, white; Cu, green; N, blue.
G
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to observe a specific “triple π−π aromatic connection” including
a phenyl group (at the silicon atom)−bipy−benzonitrile (Figure 4).
It is of note that another benzonitrile-containing compound
compound 7 contains (in addition to two 2,2′-bipyridines at
copper ions) one extra uncoordinated 2,2′-bipyridine.
At the second stage of the synthetic work similar self-assembly
reactions but in the presence of phenanthroline have been
studied. These yielded (Figure 5) the four hexacopper complexes
10−13 with a molecular architecture similar to that of the
aforementioned compounds 1−9.
(
benzonitrile/water complex 4) does not reveal such a stacking.
In turn, features of CLMSs 8 and 9 are as follows. It is known
that CLMSs often form solvates with different organic solvents.
Surprisingly, compound 8 contains no solvate molecules at all,
while water molecules are the only solvating ligands in compound 7.
This is also a quite rare feature among known CLMSs; we could
For all compounds 10−13 the charge compensation is achieved
−
by the presence of HO groups exclusively (unlike the “anion
3
7
cite only the Cu Na CLMS reported very recently. Note that
diversity” mentioned for products 1−9). In addition, products
2
2
Figure 6. π−π aromatic stacking (“phenanthroline to phenanthroline”) in complex 11. Color code: Si, yellow; O, red; Cu, green; N, blue.
Figure 7. (a) General scheme of synthesis of hexacoppersilsesquioxane containing 1,10-phenanthroline and 2,2′-bipyridine ligands 14. (b) π−π
aromatic stacking (“phenanthroline to bipyridine”) in complex 14. Color code: Si, yellow; O, red; C, black; Cu, green; N, blue.
H
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Figure 8. General scheme of synthesis of hexacoppersilsesquioxanes 15−17 containing bathophenanthroline ligands. Color code: Si, yellow; O, red;
C, black; Cu, green; N, blue.
Figure 9. Accumulation of acetophenone with time in the oxidation of
1
-phenylethanol (initial concentration was 0.33 M) with TBHP
(
1
70% aqueous; initial concentration 1.2 M) catalyzed by compounds
0 (5 × 10 M, curve 1) and 1 (5 × 10 M, curve 2; curve 2a, in the
−4
−4
presence of 0.05 M of HNO ). The solvent was acetonitrile (total
3
volume of the reaction solution was 5 mL), and the temperature was
50 °C.
1
0−13 could be easily distinguished from compounds 1−9 by
their tendency toward π−π stacking interactions of aromatic
systems of the phenanthroline ligands. While 2,2′-bipyridine-
based compounds 1−9 show no affinity for the “ligand to ligand”
packing, products 10 (solvated by DMSO) and 11 (containing no
solvates) pack in the crystal to form a ladderlike motif (Figure 6).
In turn, compounds 12 and 13 (DMF and pyridine solvates,
correspondingly) crystallize in an islandlike structure. This points
to a possible important role of solvate molecules for the
formation/cleavage of the packing. We will try to shed some light
Figure 10. Oxidation of cyclohexane (0.46 M) with H O (50%, 3 M)
2
2
−4
catalyzed by complex 10 (5 × 10 M) in the presence of HNO3
(0.05 M) at 60 °C. Concentrations of cyclohexanol (curves 1) and
cyclohexanone (curves 2) were measured both before and after
reduction with PPh3.
on this intriguing situation in our future reports. Corresponding
investigations on CLMS structure formation assisted by ligands
I
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of other types (not just of bipy family) are currently in progress
iby our team.
Catalyzed Oxidation of Alkanes with H O2 to the
2
Corresponding Alkyl Hydroperoxides. It is noteworthy that
38−40
It is interesting that our efforts in similar self-assembly
reactions with both 2,2′-bipyridine and phenanthroline simulta-
neously present in the reaction mixture resulted in the formation
of complex 14 (Figure 7a). One could expect the formation of a
product with alternating 2,2′-bipyridine- and phenanthroline-
containing CLMSs in the crystal. In reality, 14 includes both
types of ligands statistically disordered over the same structural
position. Both ligands coordinate the copper ion in the same
fashion as was described for compounds 1−13. It is worth noting
that we succeeded in the isolation of single crystals of 14 only
from a nitromethane solution. To the best of our knowledge,
product 14 is the first example of a CLMS complex with
nitromethane. Along with products 10 and 11, compound 14
demonstrates the ability to pack into an infinite ladder structure
alkanes can be oxidized
in acetonitrile solution to the corre-
sponding alkyl hydroperoxides by hydrogen peroxide in air in the
presence of catalytic amounts of complex 1, 10, 15 and nitric acid.
The alkyl hydroperoxide is relatively stable in solution and can be
easily reduced by PPh
matogram obtained after reduction with PPh
to the corresponding alcohol. The chro-
is distinguished
3
3
from the chromatogram obtained for an unreduced sample (com-
pare graphs A and B in Figure 10), which indicates that cyclohexyl
34
hydroperoxide is formed in the process. The reaction proceeds
not only at 60 °C (Figure 10) but also at 20 °C (Figure S2 in the
Supporting Information). Regioselectivity parameters in the
oxidation of n-heptane catalyzed by complex 1 are collected in
Table 1. The oxidation of cis-1,2-dimethylcyclohexane with H O
2
2
occurs without retention of configuration (the trans/cis ratio was
(
Figure 7b). It is important to emphasize the presence of two
−
Table 1. Regioselectivity Parameters in the n-Heptane
“charge compensating” CH COO moieties in the composition
3
(
0.46 M) Oxidation with H O (0.5 M) Catalyzed by
2 2
a
of this complex. Unlike the case for compound 9, these groups in
4 form tight ion pairs with the copper ions. We suggest that this
Complex 10 at 60 °C
1
difference could be explained by the similarity in molecular
geometries of nitromethane and acetate anion (∠ONO 125.9°,
entry
time, min
C(1):C(2):C(3):C(4)
1
2
3
60
180
360
1.0:5.2:5.2:4.7
1.0:5.6:5.2:6.3
1.0:6.0:5.9:7.0
∠
OCO = 129.2°). Thus, the ionic interactions could play the
principal role and, indeed, acetate anions coordinate copper
centers.
a
The selectivity parameter in the n-heptane oxidation C(1):C(2):
The self-assembly reaction approach was efficiently applied
yet another time by adding bathophenanthroline to the reac-
tion mixture. The three complexes 15−17 with the same type of
molecular topology as described for compounds 1−14 were
C(3):C(4) denotes reactivities of the H atoms at carbons 1−4
(relative to the reactivity of hydrogens at carbon 1) of the n-heptane
chain, which are normalized by taking into account the number of
hydrogen atoms at each carbon.
−
obtained (with OH groups as charge balancers, Figure 8).
a
Table 2. Oxidative Amidation at Low Catalyst Loading
To the best of our knowledge, complexes 15−17 are the first
CLMSs containing bathophenanthroline ligands. Compounds
1
5−17 show no tendency to form supramolecular aggregates
through packing.
As a short conclusion to the synthetic part of this work, it could
be also stated that formation of one and the same type of central
cage core (of Si Cu composition) for 17 products no doubt
10
6
witnesses to the high stability of such a structural unit under
conditions of the CLMS synthesis assisted by bidentate chelating
ligands of the 2,2′-bipy family. An opportunity of isolation of
another core, Me Si Cu , in the case of using a methyl-substituted
8
8
3
silane for the synthesis of the bipy derivative of Cu(II)-CLMS
ref 30) indicates the complicated character of such a type of self-
(
assembly reaction. To some extent, such a difference could be
due to steric and solubility differences for phenyl- and methyl-
based silsesquioxane matrixes. Further investigations of this
intriguing synthetic scheme deserve significant attention and are
being studied now by our team.
Catalyzed Oxidation of Alcohols to Ketones and
Benzene to Phenol. Alcohols are efficiently oxidized to the
corresponding ketones with TBHP in MeCN when complex 1 or
10 is used as a catalyst (Figure 9). The oxidation of 1-phenyl-
ethanol with TBHP at 50 °C catalyzed by 10 gave acetophenone
in 94% yield (TON = 600) after 14 h. Figure S1 in the Supporting
Information shows that aliphatic cyclohexanol is oxidized to
cyclohexanone. Complex 10 exhibited moderate activity in benzene
oxidation with H O . Thus, the reaction of benzene (0.3 M) with
2
2
−4
H O (50%, 3 M) in the presence of 10 (5 × 10 M) and HNO3
a
2
2
Reaction conditions: amine·HCl (0.5 mmol), benzyl alcohol
(
0.05 M) at 60 °C afforded phenol after 2 h in 15% yield.
(
1.0 mmol), CaCO (99.995% pure; 0.5 mmol), TBHP (5.5 M in
3
The efficiency of complex 1 turned out to be the same: the
reaction at 60 °C gave after 2 h 0.41 M (14%) of phenol and
0
nonane, 2.5 mmol), 1 or 10 (100 ppm of Cu), CH CN (1 mL), 80 °C,
24 h. Isolated yields are given. TON = (mmol of product)/(mmol of
Cu). TOF = TON/(reaction time); given in h .
3
b
c
−1
.008 M of p-quinone.
J
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Figure 11. Conversion of benzylic alcohol in the oxidative amidation reaction.
0
.7 for 1 and 10 and 0.8 for 15, where trans/cis is the ratio of
to be similar, giving secondary and tertiary amides 19−24 in
59−86% yields (Table 2). As observed previously with other
cagelike compounds, it was found possible to work with as low as
100 ppm of copper in this reaction without affecting the yields.
Moreover, turnover number (TON) and frequency (TOF)
values up to 8600 and 478 h− could be obtained, respectively,
isomers of tert-alcohols with mutual trans and cis orientation of
the methyl groups). The experiments on the methylcyclohexane
oxidations are described in Figures S3 and S4 and Tables S1−S4
in the Supporting Information. All of these peculiarities indicate
that the oxidation with H O occurs with the participation of free
1
2
2
25
−1
hydroxyl radicals.
which is significantly better than the 44 and 11 h values
26
Catalyzed Oxidation of Alcohols to Amides. Complexes
and 10 were also evaluated in the oxidative amidation of
obtained in the initial report with CuO as catalyst.
1
Discussion on Precatalyst Transformations. In order to
study the possible structural transformation of the catalyst under
catalytic act conditions, we were interested in additional studies.
To simulate the catalytic act of C−H compound oxidation, we
performed the following experiments. Successive measurements
of UV−vis spectra (for example of compound 1) were made
for (i) 1′ acetonitrile solution, (ii) this solution with nitric acid
additive, and finally (iii) the solution with hydrogen peroxide
additive. These activities provoked no significant changes in spectra
alcohols (Table 2). This reaction, initially developed using
4
1
42
43
copper, iron, and zinc salts, proved to be highly efficient
when copper silsesquioxanes were used, with catalyst loadings
down to 100 ppm of copper.
native to methodologies using expensive ruthenium and rhodium
catalysts. Thus, benzyl alcohol was reacted with several amines,
protected as their ammonium salts, in the presence of catalytic
quantities of 1 or 10 and TBHP as oxidant. Calcium carbonate,
with a high purity of 99.995% to avoid any metallic contami-
nation, was also added to slowly deprotonate the ammonium.
As demonstrated in Figure 11, oxidation of benzylic alcohol in
the presence of α-methylbenzylamine and catalyst 1 produced,
in addition to the expected benzamide 19, benzaldehyde and
benzoic acid as side products:
18a,19
This represents a good alter-
44
4
5
(
see the Supporting Information), which is not surprising, bearing
in mind the results of UV−vis experiments presented recently by
18b
some of us for Fe(III) silsesquioxane. Thus, we may conclude
that compound 1 could undergo some structural modification
during the catalytic reaction but total decomposition of cage
structure did not occur.
CONCLUSION
■
An extended series of 17 new complexes were found to be easily
available through the self-assembly reaction of in situ generated
sodium phenylsiloxanolate and copper(II) chloride in the
presence of four types of nitrogen-based ligands: 2,2′-bipyridine
(
1
compounds 1−9), 1,10-phenanthroline (compounds 10−13),
,10-phenanthroline/2,2′-bipyridine (compound 14), and bath-
Interestingly, the proportion of benzaldehyde reached a maximum
after 2 h and then slowly decreased as the quantity of benzamide
and benzoic acid increased. After 24 h of reaction, benzylic alcohol
was converted at 60% into benzamide, 24% into acid, and 6% into
benzaldehyde. This kinetic plot also shows that it is necessary to
use an excess of alcohol in this reaction, since the formation of
benzoic acid is difficult to avoid under the reaction conditions.
Even though compounds 1 and 10 have a unique structure,
their catalytic activities in the oxidative amidation were found
ophenanthroline (compounds 15−17). As was established by
single-crystal X-ray diffraction, compounds 1−17 all belong to
the same type of molecular topology despite the difference in the
N-ligand chemical nature. That no doubt points at the high
stability of such “major” type (Si Cu ) of cluster under condi-
10
6
tions of copper(II) phenylsilsesquioxane synthesis, assisted by
ligands of the bipy family. This fascinating molecular cage can be
described as a metal oxide (CuO) layer sandwiched by two pen-
6
tagonal phenylsiloxanolate [PhSiO ] ligands. Two opposite
1.5 5
K
DOI: 10.1021/acs.inorgchem.7b02320
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
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atoms of the corresponding ligand and oxygen atom of hydroxy
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Complexes 1, 10, and 15 efficiently catalyze oxidation of
alcohols to ketones with TBHP and of alkanes to alkyl hydro-
1
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2
2
apparently involves the generation of hydroxyl radicals.
Complexes 1 and 10 catalyzed the amidation of benzyl alcohols
with low catalyst loading and high turnover.
1
94.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS
Publications website at DOI: 10.1021/acs.inorgchem.7b02320.
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*
S
Details of X-ray experiments and catalytic oxidations
(
PDF)
Accession Codes
CCDC 1565028−1565032 and 1565113−1565124 contain the
supplementary crystallographic data for this paper. These data
can be obtained free of charge via www.ccdc.cam.ac.uk/
data_request/cif, or by emailing data_request@ccdc.cam.ac.uk,
or by contacting The Cambridge Crystallographic Data Centre,
2 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223
36033.
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D.; Lewis, J. E. M.; Robert, A.; Knerr-Rupp, K.; Graham, D. O.; Wright, J.
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+
R.; Giles, G. I.; Crowley, J. D. Biologically active [Pd L ] quadruply-
1
3
2 4
stranded helicates: stability and cytotoxicity. Dalton Trans. 2015, 44,
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1129−11136. (c) Ahmedova, A.; Mihaylova, R.; Momekova, D.;
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AUTHOR INFORMATION
Corresponding Authors
E-mail for A.N.B.: bilyachenko@ineos.ac.ru.
E-mail for F.L.: frederic.lamaty@umontpellier.fr.
E-mail for G.B.S.: shulpin@chph.ras.ru.
■
*
*
*
2
4
anticancer activity upon guest encapsulation. Dalton Trans. 2016, 45,
3214−13221. (d) Han, J.; Schmidt, A.; Zhang, T.; Permentier, H.;
Groothuis, G. M. M.; Bischoff, R.; Kuhn, F. E.; Horvatovich, P.; Casini,
1
̈
A. Bioconjugation strategies to couple supramolecular exo-function-
alized palladium cages to peptides for biomedical applications. Chem.
Commun. 2017, 53, 1405−1408.
ORCID
Alexey N. Bilyachenko: 0000-0003-3136-3675
Victor N. Khrustalev: 0000-0001-8806-2975
Xavier Bantreil: 0000-0002-2676-6851
Elena S. Shubina: 0000-0001-8057-3703
(5) (a) Ward, M. D.; Raithby, P. R. Functional behaviour from
controlled self-assembly: challenges and prospects. Chem. Soc. Rev.
2013, 42, 1619−1636. (b) Lu, W.; Wei, Z.; Gu, Z.-Y.; Liu, T.-F.; Park, J.;
Park, J.; Tian, J.; Zhang, M.; Zhang, Q.; Gentle, T., III; Bosch, M.; Zhou,
H.-C. Tuning the structure and function of metal−organic frameworks
via linker design. Chem. Soc. Rev. 2014, 43, 5561−5593. (c) Holloway, L.
R.; Young, M. C.; Beran, G. J. O.; Hooley, R. J. High fidelity sorting of
remarkably similar components via metal-mediated assembly. Chem. Sci.
2015, 6, 4801−4806. (d) Jansze, S. M.; Cecot, G.; Wise, M. D.; Zhurov,
K. O.; Ronson, T. K.; Castilla, A. M.; Finelli, A.; Pattison, P.; Solari, E.;
Scopelliti, R.; Zelinskii, G. E.; Vologzhanina, A. V.; Voloshin, Y. Z.;
Nitschke, J. R.; Severin, K. Ligand Aspect Ratio as a Decisive Factor for
the Self-Assembly of Coordination Cages. J. Am. Chem. Soc. 2016, 138,
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
The publication was prepared with the support of the “RUDN
University Program 5-100”, the Russian Foundation for Basic
Research (Grants 16-03-00254, 17-03-00993, 16-29-05180),
RFBR-CNRS project No. 16-53-150008, the CNRS (Programme
de Recherche Conjoint), and the University of Montpellier.
Synchrotron single-crystal diffraction measurements were per-
formed at the unique scientific facility Kurchatov Synchrotron
Radiation Source supported by the Ministry of Education and
Science of the Russian Federation (project code RFME-
FI61917X0007).
2
046−2054. (e) Metherell, A. J.; Ward, M. D. Imposing control on self-
assembly: rational design and synthesis of a mixed-metal, mixed-ligand
coordination cage containing four types of component. Chem. Sci. 2016,
7
(
, 910−915.
6) (a) Murugavel, R.; Voigt, A.; Walawalkar, M. G.; Roesky, H. W.
Hetero- and Metallasiloxanes Derived from Silanediols, Disilanols,
Silanetriols, and Trisilanols. Chem. Rev. 1996, 96, 2205−2236.
b) Lorenz, V.; Fischer, A.; Gießmann, S.; Gilje, J. W.; Gun’ko, Y.;
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