Binuclear complexes with the "Chinese lantern" geometry as intermediates in the liquid-phase oxidation of dibenzyl ether with atmospheric oxygen in the presence of copper(II) carboxylates

Article abstract of DOI:10.1134/S1070328412030086

Reactions of copper(II) carboxylates with dibenzyl ether (DBE) gave binuclear complexes of the formula Cu₂(μ-OOCR)₄(DBE) ₂ (R = Bu^t, Ph, and CF₃). The complexes were characterized by X-ray diffraction

Full text of DOI:10.1134/S1070328412030086

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2012, Vol. 38, No. 3, pp. 224–231. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © S.E. Nefedov, E.V. Kushan, M.A. Yakovleva, D.G. Chikhichin, V.A. Kotseruba, O.A. Levchenko, G.L. Kamalov, 2012, published in Koordinatsionnaya
Khimiya, 2012, Vol. 38, No. 3, pp. 233–240.
Dedicated to Professor Vladimir Fedorov
on the occasion of his 75th birthday
Binuclear Complexes with the “Chinese Lantern” Geometry
as Intermediates in the LiquidꢀPhase Oxidation of Dibenzyl Ether
with Atmospheric Oxygen in the Presence of Copper(II) Carboxylates
S. E. Nefedova, *, E. V. Kushana, M. A. Yakovlevaa, D. G. Chikhichinb, V. A. Kotserubab,
O. A. Levchenkob, and G. L. Kamalovb, *
a Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
b Bogatskii Physicochemical Institute, National Academy of Sciences of Ukraine, Odessa, Ukraine
*eꢀmail: snef@igic.ras.ru; gerbert_kamalov@ukr.net
Received September 29, 2011
Abstract—Reactions of copper(II) carboxylates with dibenzyl ether (DBE) gave binuclear complexes of the
formula Cu2(µ
ꢀOOCR)4(DBE)2 (R = But, Ph, and CF3). The complexes were characterized by Xꢀray difꢀ
fraction. The axial positions in the lanternꢀtype dimer are occupied by the coordinated DBE molecules. The
complexes seem to be analogs of intermediate catalysts for the oxidation of DBE with atmospheric oxygen in
the presence of transition metal complexes. When stored in air, the complex Cu2( ꢀOOCPh)4(DBE)2 underꢀ
went oxidation into Cu2( ꢀOOCPh)4(HOOCPh)2, which was characterized by Xꢀray diffraction. The geomꢀ
µ
µ
etry of its framework is similar; the structure is stabilized by intramolecular H bonds between the axially oriꢀ
ented benzoic acid molecules and the adjacent bridging benzoate anions.
DOI: 10.1134/S1070328412030086
Investigations of the main pathways of liquidꢀphase tors that influence the activity and selectivity of metalꢀ
oxidation of dibenzyl ether (DBE) with atmospheric
oxygen (hereafter, air) in the presence of metal comꢀ
plexes [1] are largely motivated by the need of catalytic
methods for the recovery of DBE, which is a waste
product in the largeꢀcapacity production of such chemꢀ
icals as benzyl alcohol (BAlc), benzyl benzoate (BB),
complex catalysts for liquidꢀphase oxidation of organic
substrates containing an activated CH bond [1].
In the study of the catalytic properties of polynuclear
carboxylates of 3d metals [8–15], particular emphasis
has been placed on alternative pathways of the liquidꢀ
phase oxidation of DBE and the decomposition of HP,
varying with the structure and composition of the startꢀ
ing metal complex and the reaction conditions.
benzoic acid (BAc), and benzylcellulose [2⎯4]. In addiꢀ
tion, DBE is a byꢀproduct in the preparation of benzylꢀ
containing phenols, amides, amines, etc. [5–7]. Furꢀ
thermore, because DBE is readily oxidizable and
because its monohydroperoxide (HP) is fairly stable,
the process under discussion can be regarded as a conꢀ
It has been found that the oxidation of DBE with
air in the presence of a metal complex (more than
venient model reaction for revealing the structural facꢀ 250 complexes studied) follows the scheme:
O
2
2PhCHO
BAld
2PhCOOH
BAc
O
2
2
(1)
(2)
O
PhCH2OCH2Ph
DBE
PhCH(OOH)OCH2Ph –H O
2
O
2
HP
PhCOOCH2Ph
BB
PhCHO
BAld
In this case, the dehydration of HP to BB usually
proceeds at a rate of three to five times lower; when the
conversion of DBE is less than 10–15%, the reaction
DBE → HP → 2BAld → 2BAc.
It has been also found that the activities of the comꢀ
sequence can be schematically represented as follows: plexes studied in each step of sequence (2) change in a
224

BINUCLEAR COMPLEXES WITH THE “CHINESE LANTERN” GEOMETRY
225
similar way. Therefore, at a low conversion of DBE, the
3dꢀmetal carboxylateꢀcatalyzed liquidꢀphase oxiꢀ
the formation and dehydration of HP, as well as the dation of DBE with air.
oxidation of benzaldehyde (BAld) to BAc, can occur
at the same “catalytic center” (metal center). Accordꢀ
ing to the scheme proposed by us for alternative cataꢀ
lytic cycles of BAld formation, the terminal ligands in
the starting complex (Cat) can be replaced by DBE
and its coordinated (activated) molecule in the comꢀ
Here we describe the synthesis and structures of
possible intermediates of the catalytic oxidation of
DBE with air: the adducts of the formulas Cu2(
μꢀ
ꢀ
OOCR)4(DBE)2 (R = But, Ph, and CF3) and Cu2(
μ
OOCPh)4(BAc)2
.
plex DBE
dioxygen coming from either the bulk or the complex
DBE Cat О2
According to the kinetic data for the decomposiꢀ
tion of HP in DBE oxidate in an inert atmosphere
(when BB is the major product), the rateꢀlimiting step
of the process in the catalytic systems studied (Cat'
that are derived from the starting metal complexes
under the action of the components of the reaction
mixture) is the formation of the intermediate comꢀ
⋅ Cat will be oxidized into HP with
EXPERIMENTAL
⋅
⋅
.
Aqueous cupric acetate was used without further
purification. Dibenzyl ether was purified by distillaꢀ
tion in vacuo in an inert atmosphere as described in
[16]. All manipulations involving the synthesis and
isolation of the complexes were carried out under pure
argon in dehydrated solvents, unless otherwise speciꢀ
fied.
Synthesis of Cu2(μ . A. The
ꢀOOCBut)4(DBE)2 (I)
plexes HP
the oxidate (P) can also act as catalyst poisons by
forming the complexes P Cat'. We have also assumed
⋅ Cat'. At the same time, the components of
complex Cu2(OOCBut)4(NEt3)2 (0.2 g, 0.27 mmol)
was dissolved in dibenzyl ether (10 mL) and heated in
air at 165°С for 0.5 h. The resulting homogeneous
solution was slowly to room temperature while graduꢀ
ally cooling the oil bath. The blueꢀgreen crystals that
formed were separated from the mother liquor by
decantation, successively washed with cold benzene
and hexane, and dried under argon. The yield of comꢀ
⋅
that the observed differences in the properties of the
complexes studied in the liquidꢀphase oxidation of
DBE and in the decomposition of HP are due to a
competition for the “catalytic center” between HP
and dioxygen.
Recently [16], we have found that a reaction of the
polymer complex [FeCl2(NCMe)2]n with 3,5ꢀdimethꢀ
ylpyrazole (HDmpz) yields a tetrahedral complex of
the formula [Fe(HDmpz)3Cl]Cl, which is oxidized
with air in acetonitrile into the binuclear complex
plex
B. Cupric pivalate (0.2 g, 0.75 mmol) was dissolved
in acetonitrile (10 mL) and crystallized at –5 . The
I was 0.038 g (15%).
°С
small crystals that formed were separated from the
faintly colored mother liquor by decantation. Then
dehydrated DBE (10 mL) was added and the resulting
[Fe(HDmpz)3Cl2]2(
be obtained by a reaction of FeCl3
μ
ꢀO) (А). The same complex can
⋅
6H2O with
suspension was stirred at 60
°
С
to homogenization.
HDmpz. However, oxidation of complex A with air in
The solution was kept at +5
°
С for 24 h. The blueꢀ
a solution of DBE in CH2Cl2 gives the complex
green crystals that formed were separated from the
mother liquor by decantation, successively washed
with cold benzene and hexane, and dried under argon.
(
(HDmpz)FeCl2[η2ꢀN,Oꢀ(Dmpz)C(O)H(Ph)] (B)
)
containing the coordinated tetrahedral intermediate
in the condensation of HDmpz with BAld (Schemes 1
and 2).
The yield of complex I was 0.296 g (85%).
The structures of the complexes under discussion
were confirmed by Xꢀray diffraction data.
Note that complex B is the first example of interꢀ
mediate complexes capable of forming from the prodꢀ
ucts of the liquidꢀphase oxidation of DBE with air
under the conditions of metalꢀcomplex catalysis.
For C48H64O10Cu2 (
anal. calcd., %:
Found, %:
M
= 928.07)
C, 62.12;
C, 61.85;
H, 6.95.
H, 6.73.
IR (cm–1): 3071 w, 2554 w, 1715 w, 1677 s, 1608 m,
1583 m, 1569 m, 1497 w, 1452 m, 1471 m, 1404 m,
1320 m, 1271 s, 1178 m, 1070 m, 1052 s, 1000 w,
931 m, 842 w, 804 m, 705 s, 683 s, 667 m, 616 w.
Synthesis of Cu2(
Cupric benzoate (0.2 g, 0.65 mmol) was dissolved in
acetonitrile (15 mL) and crystallized at –5 . The
small crystals that formed were separated from the
faintly colored mother liquor by decantation. Then
dehydrated DBE (10 mL) was added and the resulting
Ph
CH
N
N
O
Fe
N
Cl
Cl
μꢀOOCPh)4(DBE)2 ⋅ DBE (II).
°С
HN
(B)
suspension was stirred at 60
°С
to homogenization.
The aforesaid results and assumptions served as a The solution was kept at +5°С for 24 h. The blueꢀ
main prerequisite for revealing the possibility of isolaꢀ green crystals that formed were separated from the
tion and identification of intermediate complexes in mother liquor by decantation, successively washed
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 38
No. 3
2012

226
NEFEDOV et al.
with cold benzene and hexane, and dried under argon. monochromator,
ω scan mode). The structures of the
The yield of complex II was 0.314 g (80%).
complexes were calculated with the SHELXTL PLUS
program package (PC version) and refined with the
SHELXTLꢀ97 program [17, 18]. Crystallographic
parameters and the data collection and refinement
statistics are summarized in table. The comprehensive
tables of the atomic coordinates, bond lengths, and
For C70H62O11Cu2 (
anal. calcd., %:
Found, %:
M
= 1206.28)
C, 69.69;
C, 69.50;
H, 5.18.
H, 4.99.
bond angles in structures I–IV have been deposited
IR (cm–1): 3571 w, 3064 w, 1593 m, 1548 s, 1494 w,
1417 s, 1360 w, 1312 w, 1270 w, 1207 w, 1094 m,
1064 m, 1027 m, 952 w, 806 w, 737 m, 695 s, 607 w.
with the Cambridge Crystallographic Data Collection
(nos. 856456–856459; deposit@ccdc.cam.ac.uk or
http://www.ccdc.cam.ac.uk/data_request/cif).
Synthesis of Cu2(μꢀOOCCF3)4(DBE)2 (III). Aqueꢀ
ous cupric acetate (0.2 g, 1 mmol) was dissolved in
boiling trifluoroacetic acid (5 mL) and allowed to cool
to room temperature in the bath. The precipitate that
RESULTS AND DISCUSSION
Dissolution
OOCBut)4(NEt3)2 in DBE followed by heating in air to
165 and by slow cooling to room temperature gave
complex in a rather low yield (15%). However, when
of
the
complex
Cu2(μꢀ
formed was dissolved at 80
and kept in a refrigerator at –5
°
С
in acetonitrile (10 mL)
. The resulting fine
°
С
°С
crystalline product was separated from the mother
liquor by decantation. Then dehydrated DBE (10 mL)
was added and the resulting suspension was stirred in
I
the starting adducts contained more labile terminal
ligands (acetonitrile) than triethylamine, the yields of
air at 60
°
С
to homogenization. The solution was kept
the complexes Cu2(
noticeably higher (45–85%) even under milder condiꢀ
tions (60 ).
μꢀOOCR)4(DBE)2 (I–III) were
at +5°С for 24 h. The blueꢀgreen crystals that formed
were separated from the mother liquor by decantation,
successively washed with cold benzene and hexane,
and dried under argon. The yield of complex III was
0.209 g (45%).
°
С
R
R
C
C
O
O
O
O
Cu
L
Cu
O
For Cu2C32H28O10F12
anal. calcd., %:
Found, %:
(
M
= 975.66)
L
C, 41.43;
C, 41.28;
H, 3.04.
H, 2.89.
O
O
O
C
C
R
R
IR (cm–1): 1648, 1575 s, 1534 s, 1496 w, 1470 w,
1414 m, 1357 w, 1196 s, 1150 s, 1034 w, 1022 m, 951 w,
878 w, 857 m, 793 m, 746 m, 732 s, 694 s, 621 w, 601 w.
R
R
C
C
Synthesis of Cu2(μꢀOOCPh)4[OC(OH)Ph]2 (IV).
O
O
O
O
The flask with the mother liquor of complex II was
filled with air, sealed, and kept at room temperature
for a month. The large green crystals that formed over
the solution were isolated mechanically.
CH2
DBE
–L
CH2
CH2
Cu
O
CH2
Cu
O
O
O
O
O
C
C
R
R
For Cu2C42H32O12
anal. calcd., %:
Found, %:
(
M = 855.76)
C, 58.95;
H, 3.77.
H, 3.60.
Note that the yields of complexes I–III correlate
C, 58.79;
with the basicities of the corresponding carboxylate
−
anions in the starting complexes: But − > Ph
>
CO2
CO2
IR (cm–1): 3030 w, 2911 w, 2659 w, 2549 w, 1718 w,
1676 m, 1609 m, 1601 w, 1583 w, 1568 m, 1500 w,
1452 w, 1386 s, 1318 m, 1273 m, 1212 w, 1178 w,
1164 w, 1145 w, 1125 w, 1097 w, 1070 m, 1025 m,
1 0 0 1 w, 9 4 5 w, 9 3 0 w, 8 5 3 m , 8 4 2 w, 8 3 3 w, 8 1 9 w, 8 0 5 w,
725 m, 709 s, 693 s, 681 s, 659 m, 617 w.
IR spectra were recorded on a NexusꢀNicolet
FTIR spectrophotometer in the 400–4000 cm–1 range
by using frustrated total internal reflection from a sinꢀ
gle crystal of a test complex.
−
F C
3
CO2.
According to Xꢀray diffraction data, complexes
I–
III (Figs. 1–3) are traditional lanternꢀtype dimers
with a short nonbonding metal–metal distance
dependent on the substituent R in the bridging carboxꢀ
ylate anions: the Cu⋅⋅⋅Cu distance in the complex with
the pivalate anion (2.5692(7) Å) is somewhat shorter
than those in the case of the electronꢀwithdrawing
benzoate and trifluoroacetate anions
(Cu⋅⋅⋅Cu
Xꢀray diffraction study was carried out on a Bruker 2.5813(8) and 2.6882(18) Å, respectively), while the
SMART Apex II automated diffractometer equipped Cu–O bond lengths do not differ greatly (1.929(3)–
with a CCD detector (MoКα radiation, graphite 1.976(5) Å).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 38
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2012

BINUCLEAR COMPLEXES WITH THE “CHINESE LANTERN” GEOMETRY
227
Crystallographic parameters and the data collection and refinement statistics for structures I–IV
Value
Parameter
I
II
III
IV
Temperature, K
Crystal system
Space group
120(2)
100(2)
150(2)
100(2)
Triclinic
Monoclinic
Monoclinic
2/
Monoclinic
P–
1
P
21
C
c
P21/n
Unit cell parameters
a
, Å
, Å
11.5242(16)
11.7479(16)
19.439(3)
98.900(2)
106.403(2)
101.476(2)
2411.1(6)
2
10.4206(15)
27.226(4)
10.6230(15)
90
10.310(4)
20.876(8)
18.768(8)
90
10.6181(11)
11.6145(12)
15.1774(16)
90
b
c
, Å
, deg
, deg
, deg
α
β
106.172(2)
90
93.657(7)
90
91.219(2)
90
γ
V
Z
, Å3
2894.6(7)
2
4031(3)
1871.3(3)
2
4
ρcalcd, mg/m3
, mm–1
(000)
Crystal dimensions, mm
scan range, deg
Ranges of , and
ces
1.278
1.384
1.608
1.164
1960
0.16
1.519
μ
0.935
0.799
1.203
F
980
1256
876
0.14
×
0.12
×
0.10
0.14
×
0.12
×
0.10
0.18
×
×
0.14
0.16
× 0.14 × 0.12
θ
1.82–26.00
2.42–26.00
2.17–26.99
2.68–27.00
h
,
k
l
indiꢀ
–14
–14
–23
≤
≤
≤
h
k
l
≤
≤
≤
14,
14,
23
–12
–33
–13
≤
≤
≤
h
k
l
≤
≤
≤
12,
33,
13
–13
–24
–23
≤
≤
≤
h
k
l
≤
≤
≤
13,
26,
22
–13
–14
–19
≤
≤
≤
h
k
l
≤
≤
≤
13,
14,
19
Number of measured reꢀ
flections
21461
25773
12245
17180
Number of independent
reflections
9435 (
R
int = 0.0921) 11267 (
Rint = 0.0778) 4334 (
R
int = 0.0797) 4012 (
Rint = 0.0752)
GOOF
0.951
1 = 0.0487,
wR2 = 0.0804
1 = 0.1089,
0.965
1.127
0.975
1 = 0.0517,
wR2 = 0.1110
1 = 0.0998,
R
(
I
> 2
(for all reflections)
Δρmin
A–3
σ(I
))*
R
R
1 = 0.0525,
wR2 = 0.0756
R
1= 0.0849,
wR2 = 0.2022
R
R
R
R
1 = 0.0979,
wR2 = 0.0896
R
1 = 0.1629,
wR2 = 0.2504
R
wR2 = 0.0946
wR2 = 0.1330
Δρmax
/
,
e
1.421/–0.970
0.294/–0.349
0.966/–1.160
0.771/–0.518
2
*
R
= |Σ
||F
| – |F
||/
Σ| ; wR2 = {
F |
Σ
[
w(
Fo2
–
Fc2) ]/
Σ
w(
Fo2) }
2 1/2
.
1
o
c
o
The apical position in the tetragonalꢀpyramidal benzoate anions (angle PhC(2)–C(7)/PhC(51)–C(58) 2.1°,
environment of each Cu(II) atom copper in the binuꢀ
clear complex are occupied by the O atoms of the
coordinated DBE molecule. The corresponding Cu–
O bond lengths also vary with the substituent in the
carboxylate anion (2.178(3) and 2.196(3) Å for R =
But and 2.107(6) and 2.146(6) Å for R = CF3). In comꢀ
plex II, the Cu–ODBE bonds are longer (2.219(3)
CPhC(2)–C(7)⋅⋅⋅CPhC(51)–C(58) 3.415(7)–3.481(7) Å;
angle PhC(9)–C(14)/PhC(30)–C(35) 6.1 CPhC(9)–C(14)⋅⋅⋅
°,
CPhC(30)–C(35) 3.509(7)–3.538(7) Å). The crystal unit
cell of complex II contains a solvate DBE molecule,
which is out of contact with other molecules in the
unit cell; this DBE molecule is geometrically similar
to the coordinated DBE molecules (in II: O(11)–C,
1.417(5) and 1.442(5) Å; O(9)–C, 1.441(5) and
and 2.204(3) Å) than those in complexes
I and
III. Apparently, this is due to contacts between the
benzene rings of the coordinated DBE molecules
1.454(5) Å; O(10)–C, 1.433(5) and 1.444(5) Å; in III
:
(Fig. 4) and the phenyl substituents of the bridging O(5)–C, 1.452(7) Å; O(6)–C, 1.424(7) Å; in
I:
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 38
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2012

228
NEFEDOV et al.
C(32)
C(19)
C(33)
C(18)
C(31)
C(20)
C(3)
C(17)
C(16)
C(34)
C(29)
C(30)
C(38)
O(7)
C(39)
C(40)
O(8)
C(4)
C(1)
C(37)
C(2)
C(5)
C(28)
C(21)
C(13)
O(1)
Cu(1)
C(27)
O(9)
O(5)
C(35)
C(22)
O(2)
C(36)
C(41)
C(26)
Cu(2)
O(10)
C(11)
C(12)
O(6)
C(23)
O(3)
C(42)
C(43)
O(4)
C(8)
C(25)
C(6)
C(24)
C(15)
C(48)
C(14)
C(7)
C(44)
C(9)
C(47)
C(10)
C(45)
C(46)
Fig. 1. Structure @I with atomic thermal displacement ellipsoids (30% probability). Selected bond lengths and bond angles:
Cu(1)⋅⋅⋅Cu(2), 2.5692(7) Å; Cu(1)–O(1), 1.939(3) Å; Cu(1)–O(3), 1.973(3) Å; Cu(1)–O(5), 1.942(3) Å; Cu(1)–O(7),
1.974(3) Å; Cu(2)–O(2), 1.975(3) Å; Cu(2)–O(4), 1.929(3) Å; Cu(2)–O(6), 1.972(3) Å; Cu(2)–O(8), 1.932(3) Å; Cu(1)–O(9),
2.196(3) Å; Cu(2)–O(10), 2.178(3) Å; O(1)Cu(1)Cu(2), 86.58(8)°; O(3)Cu(1)Cu(2), 84.25(8)°; O(5)Cu(1)Cu(2), 86.15(8)°;
O(7)Cu(1)Cu(2), 82.49(8)°; O(9)Cu(1)Cu(2), 176.09(7)°; O(2)Cu(2)Cu(1), 83.05(8)°; O(4)Cu(2)Cu(1), 85.37(8)°;
O(6)Cu(2)Cu(1), 83.51(8)°; O(8)Cu(2)Cu(1), 87.15(8)°; O(10)Cu(2)Cu(1), 177.97(7)°.
O(9)⎯C, 1.431(6) and 1.443(6) Å; O(10)–C, 1.435(6) (deadlock) product of the catalytic oxidation of DBE
and 1.444(6) Å).
with air, will most likely decrease the effective concenꢀ
tration of catalytic intermediates such as, e.g., comꢀ
plexes I–III.
It should be emphasized that although lanternꢀtype
copper(II) complexes containing weak Oꢀdonors
in the axial position are well studied [24–30], comꢀ
plexes I–III we characterized here are the first examꢀ
ples of stable transition metal complexes with dibenzyl
ether.
As noted above, air exposure of the reaction mixꢀ
ture containing complex II at room temperature for a
month results in the formation of green single crystals
of complex IV. According to Xꢀray diffraction data
(Fig. 5), the latter is also a binuclear lanternꢀtype
dimer with two axially coordinated BAc molecules
(Cu⋅⋅⋅Cu 2.5996(9) Å; Cu(1)–O(1), 1.944(3) Å;
Cu(1)–O(2), 1.991(3) Å; Cu(1)–O(3), 2.179(3) Å;
Cu(1)–O(5), 1.951(3) Å; Cu(1)–O(6), 1.950(3) Å).
The Cu–O(2) bond is slightly longer than the other
metal–oxygen bonds in the tetrabridged dimer, probꢀ
ably because of the hydrogen bonding between the carꢀ
boxyl groups of BAc (Cu–O, 2.179(3) Å) and the O(2)
ACKNOWLEDGMENTS
This work was supported by the Russian Foundaꢀ
tion for Basic Research (project nos. 10ꢀ03ꢀ90420, 11ꢀ
03ꢀ00824, and 11ꢀ03ꢀ01157), the Competition of
Research Projects Shared by the Russian Foundation
for Basic Research and the National Academy of Sciꢀ
ences of Ukraine (project no. 21ꢀ10), and the Presidꢀ
ium of the Russian Academy of Sciences and the Diviꢀ
sion of Chemistry and Materials Sciences of the Rusꢀ
sian Academy of Sciences (Programs “Theoretical
and O(2
zoate anions (
result, the coordinated BAc molecules are coplanar
with the fragment Cu2( ꢀOOCPh)2
A
) atoms of the corresponding bridging benꢀ
O
⋅⋅⋅O 2.715(4), H–O 1.78 Å). As a
μ
.
According to Xꢀray diffraction data at 100 K, the
geometry of complex IV is almost identical with its
roomꢀtemperature geometry [19].
In contrast to lanternꢀtype dimers in which hydroꢀ and Experimental Study of the Nature of Chemical
gen bonding (like that in complex IV) activates the axiꢀ Bonding and the Mechanisms of the Essential Chemꢀ
ally coordinated organic molecules [20–23], the coorꢀ ical Reactions and Processes” and “Targeted Syntheꢀ
dinated benzoic acid in complex IV, which is the final sis of Inorganic Compounds and Creation of Funcꢀ
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 38
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2012

BINUCLEAR COMPLEXES WITH THE “CHINESE LANTERN” GEOMETRY
229
C(19)
C(20)
C(18)
C(21)
C(40)
C(39)
C(17)
C(41)
C(16)
C(42)
C(38)
C(37)
O(9)
O(5)
C(15)
C(13)
C(36)
C(29)
C(14)
C(12)
O(6)
O(3)
C(11)
C(52)
C(53)
C(56)
C(8)
C(35)
Cu(1)
C(34)
C(54)
C(55)
C(9)
C(30)
C(10)
O(1)
O(4)
C(31)
C(3)
C(51)
C(50)
C(2)
C(33)
Cu(2)
C(1)
O(7)
C(22)
C(32)
C(4)
C(5)
O(2)
O(10)
C(7)
C(43)
C(44)
O(8)
C(23)
C(28)
C(6)
C(24)
C(49)
C(45)
C(25)
C(46)
C(48)
C(47)
C(26)
C(27)
Fig. 2. Structure II with atomic thermal displacement ellipsoids (50% probability). Selected bond lengths and bond angles:
Cu(1)⋅⋅⋅Cu(2), 2.5813(8) Å; Cu(1)–O(1), 1.948(3) Å; Cu(1)–O(3), 1.947(3) Å; Cu(1)–O(5), 1.960(4) Å; Cu(1)–O(7),
1.953(3) Å; Cu(1)–O(9), 2.204(3) Å; Cu(2)–O(2), 1.941(3) Å; Cu(2)–O(4), 1.952(3) Å; Cu(2)–O(6), 1.959(4) Å; Cu(2)–O(8),
1.961(3) Å; Cu(2)–O(10), 2.219(3) Å; O(1)Cu(1)Cu(2), 81.69(11)°; O(3)Cu(1)Cu(2), 87.11(11)°; O(7)Cu(1)Cu(2),
82.70(10)°; O(5)Cu(1)Cu(2), 86.89(11)°; O(9)Cu(1)Cu(2), 174.81(9)°; O(2)Cu(2)Cu(1), 87.88(11)°; O(4)Cu(2)Cu(1),
82.90(11)°; O(6)Cu(2)Cu(1), 83.02(11)°; O(8)Cu(2)Cu(1), 87.44(11)°; O(10)Cu(2)Cu(1), 175.22(9)°.
F(6A
)
C(16A)
C(15A)
F(4A)
F(5
A)
C(17A)
C(4A)
F(1
A)
C(14
A)
F(3A
)
C(3A)
C(10A)
O(4A)
C(18A)
C(9
A
)
O(3
A)
C(13
C(12
O(6)
O(2)
A)
C(11A)
C(2
A
)
O(2A)
A
)
C(1A)
F(2A)
C(12)
C(13)
C(8
A
)
Cu(2)
C(6A)
O(1A)
C(7A)
C(18)
C(17)
C(5A)
Cu(1)
F(2)
O(5)
O(1)
C(14)
C(1)
O(4)
C(3)
C(5)
C(6)
O(3)
C(2)
F(3)
C(16)
F(5)
C(4)
C(7)
C(15)
C(11)
F(1)
F(6)
F(4)
C(8)
C(10)
C(9)
Fig. 3. Structure III with atomic thermal displacement ellipsoids (30% probability). Selected bond lengths and bond angles:
Cu(1) Cu(2), 2.6882(18) Å; Cu(1)–O(1), 1.967(6) Å; Cu(1)–O(1 ), 1.967(6) Å; Cu(1)–O(3), 1.960(5) Å; Cu(1)–O(3 ),
1.960(5) Å; Cu(1)–O(5), 2.107(6) Å; Cu(2)–O(2), 1.966(5) Å; Cu(2)–O(2 ), 1.966(5) Å; Cu(2)–O(4), 1.976(5) Å;
Cu(2) O(4 ), 1.976(5) Å; Cu(2)–O(6), 2.146(5) Å; O(1)Cu(1)Cu(2), 82.73(16)°; O(1 )Cu(1)Cu(2), 82.73(16)°;
O(3)Cu(1)Cu(2), 84.64(14)°; O(3 )Cu(1)Cu(2), 84.64(14)°; O(5)Cu(1)Cu(2), 180.0°; O(2)Cu(2)Cu(1), 83.98(13)°;
O(2 )Cu(2)Cu(1), 83.98(13)°; O(4)Cu(2)Cu(1), 82.53(12)°; O(4 )Cu(2)Cu(1), 82.53(12)°; O(6)Cu(2)Cu(1), 180.0°.
⎯
A
A
A
⎯
A
A
A
A
A
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 38
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2012

230
NEFEDOV et al.
C(70B)
C(69
B)
C(39E)
C(40
E)
C(39G)
C(40G)
C(58B)
C(68
B
)
C(65
)
B)
C(39I)
C(40I)
O(11
B
C(41E)
O(11C)
C(41
G)
C(66
C(35
B
)
O(11D)
C(38E)
C(67B)
C(41
I)
C(38
G
)
C(13G)
C(42E)
C(38I)
O(37
C(36
O(9
Cu(1
E)
C(42
G)
E
)
C(13I)
C(42
I
C(14
)
C(35G)
C(37G)
C(29E)
C(14
G
)
E
)
C(35I)
C(29G)
I)
C(37
C(36
O(9
I)
C(36
O(9
G
)
E)
O(3
E
)
)
C(34
I
)
C(29
I
)
I
)
C(30E)
C(9G)
O(3
G
)
G
)
E
)
O(9
I
)
C(30
C(31
G)
I)
O(7E)
O(3I)
Cu(1G)
O(5E
C(30I)
O(4E)
C(10G)
Cu(1
I
)
C(8
O(4
G
G
)
O(5
G)
C(31E)
)
C(33I)
C(32
E
C(8
I)
G)
)
O(5I)
C(32G)
C(31
I
)
C(32
I
)
O(4
I)
C(53G)
O(1E)
O(1
G
)
O(8E)
O(1
I
)
C(3E)
C(52
G
)
C(53I)
O(6E)
O(8G)
C(1
G
)
C(52
C(51
C(50
I)
O(6
G
)
C(3
G
)
Cu(1
O(2E)
O(10
E
E)
)
O(8
I
)
C(3
I)
Cu(2G)
O(2G)
O(10
I)
C(2
E)
Cu(2
O(10
I)
I)
C(51
C(50
C(43G)
G)
G)
C(1
C(2I
I)
C(4E)
C(2
G
)
I
)
I)
)
O(2
G)
C(7E
)
C(4
I
)
C(56G)
C(49G)
C(43
C(44
I
)
C(56
I)
C(7
G
)
C(5E
)
C(7
I
)
C(44
G)
C(49
I
)
C(6E)
C(5
G)
I
)
C(5I)
C(6G)
C(45
G)
C(6I)
C(48G)
C(45I)
C(48I)
C(46G)
C(47G)
C(47I)
C(46I)
Fig. 4. Fragment of the packing of structure II
.
C(19)
C(18)
C(20)
C(17)
C(12A)
C(16)
C(13A)
C(21)
C(4A)
C(14A)
C(3
A)
C(15)
O(5)
C(11A)
O(6
A)
C(5A)
C(8A)
O(3
A)
C(2
)
A)
C(9A)
C(10A)
O(1A)
C(1A
Cu(1A)
O(4A)
C(6A)
O(2)
H(4BA
)
C(7A)
C(7)
H(4B)
O(2
A)
C(2)
C(6)
O(4)
C(9)
Cu(1)
C(1)
O(1)
O(5
C(10)
C(11)
O(3) C(8)
A)
C(14)
C(3)
C(5)
C(4)
O(6)
C(15A)
C(13)
C(12)
C(16A)
C(21A)
C(17A)
C(20A)
C(18A)
C(19A)
…
Fig. 5. Structure IV. Selected bond lengths and bond angles: Cu(1) Cu(1
A
), 2.5996(9) Å; Cu(1)–O(1), 1.944(3) Å; Cu(1)–O(2),
), 85.50(8)°;
), 85.77(8)°.
1.991(3) Å; Cu(1)–O(3), 2.179(3) Å; Cu(1)–O(5), 1.951(3) Å; Cu(1)–O(6), 1.950(3) Å; O(1)Cu(1)Cu(1
O(2)Cu(1)Cu(1 ), 83.83(8)°; O(3)Cu(1)Cu(1 ), 174.55(8)°; O(5)Cu(1)Cu(1 ), 83.60(8)°; O(6)Cu(1)Cu(1
A
A
A
A
A
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 38
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2012

BINUCLEAR COMPLEXES WITH THE “CHINESE LANTERN” GEOMETRY
231
14. Chikhichin, D.G., Kotseruba, V.A., Levchenko, O.A.,
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tional Materials”, the Council of Grantd of the Presiꢀ
dent of the Russian Federation (MKꢀ555.2011.3).
et al., Teor. Eksp. Khim., 2010, vol. 46, no 1, p. 14.
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2012