Osmium(IV) binuclear nonelectrolytic oxo-bridged carboxylates. Molecular structure of [Os2IV(μ-O)(μ-O2CCCl 3)2Cl4(PPh3)2] ·CH2Cl2

Article abstract of DOI:10.1023/B:RUCO.0000022801.63892.43

The reactions between trans-[Os^VIO₂Cl ₂L₂] (L = PPh₃, AsPh₃, SbPh ₃) and carboxylic acids RCO₂H (R = CH₃, C(CH₃)₃, CH₂Cl, CCl₃, CF ₃) are studied. The resulting binuclear compounds were found to have the general formula [Os₂^IV(μ-O)(μ-O ₂CR)₂Cl₄(L)₂] (L = PPh₃; R = CH₃, C(CH₃)₃, CH₂Cl, CCl ₃, CF₃, and L = AsPh₃; R = CH₃, CH₂Cl, CCl₃, CF₃). X-ray diffraction analysis revealed that the [Os₂^IV(μ-O)(μ-O ₂CCCl₃)₂Cl₄(PPh₃) ₂]·CH₂Cl₂ complex crystallizes in a triclnic system with space group P1 ; a = 10.747(2) A, b = 19.291(4) A, c = 24.614(5) A, α = 100.08(3)°, β = 90.63(3)°, γ = 97.05(3)°, V = 4983.5(17) A³, Z = 4. The Os(μ-O)Os angle is 142.2(7)°. The interaction of trans-[Os ^VIO₂Cl₂(SbPh₃)₂] with all the acids under study is attended by intramolecular redox reaction resulting in SbCl₂Ph₃.

Full text of DOI:10.1023/B:RUCO.0000022801.63892.43

Russian Journal of Coordination Chemistry, Vol. 30, No. 4, 2004, pp. 262–268. Translated from Koordinatsionnaya Khimiya, Vol. 30, No. 4, 2004, pp. 281–287.
Original Russian Text Copyright © 2004 by Belyaev, Eremin, Simanova, Evreinova.
Osmium(IV) Binuclear Nonelectrolytic Oxo-Bridged
Carboxylates. Molecular Structure
of [OsI2V(m-O)(m-O2CCCl3)2Cl4(PPh3)2] · CH2Cl2
A. N. Belyaev, A. V. Eremin, S. A. Simanova, and N. V. Evreinova
St. Petersburg State Technological Institute (Technical University), Moskovskii pr. 26, St. Petersburg, 198013 Russia
Received October 23, 2003
Abstract—The reactions between trans-[OsVIO2Cl2L2] (L = PPh3, AsPh3, SbPh3) and carboxylic acids RCO2H
(R = CH3, C(CH3)3, CH2Cl, CCl3, CF3) are studied. The resulting binuclear compounds were found to have the
general formula [OsIV(µ-O)(µ-O2CR)2ël4(L)2] (L = PPh3; R = CH3, ë(ëç3)3, CH2Cl, CCl3, CF3, and L =
2
AsPh3; R = CH3, CH2Cl, CCl3, CF3). X-ray diffraction analysis revealed that the [OsIV(µ-O)(µ-
2
O2CCCl3)2ël4(PPh3)2] · CH2Cl2 complex crystallizes in a triclinic system with space group P1 ; a = 10.747(2) Å,
b = 19.291(4) Å, c = 24.614(5) Å, α = 100.08(3)°, β = 90.63(3)°, γ = 97.05(3)°, V = 4983.5(17) Å3, Z = 4. The
Os(µ-O)Os angle is 142.2(7)°. The interaction of trans-[OsVIO2Cl2(SbPh3)2] with all the acids under study is
attended by intramolecular redox reaction resulting in SbCl2Ph3.
The binuclear µ-oxocarboxylates containing the obtained compounds are substantially influenced by the
bent M2(µ-O) metal core are of interest for researchers nature of L in trans-[OsO2Cl2L2] and of R in the bridged
due to their structural conformity to some metal
enzymes, such as hemerythrine, and due to their pecu-
liar magnetic, spectral and redox properties [1, 2].
carboxylates µ-RCO2 [11].
The aim of this work was to study the reaction
between trans-[OsVIO2Cl2L2] (L = PPh3, AsPh3, SbPh3)
The Cr, Mn, Fe, V, Ti, and Ru complexes were syn- and carboxylic acids RCO2H (R = CH3, C(CH3)3,
thesized and studied in [1–9], while investigations con- CH2Cl, CCl3, CF3).
cerned with the diosmium complexes of this type were
only reported in two papers [10, 11].
RESULTS AND DISCUSSION
When trans-[OsVIO2Cl2L2] (L = PPh3, AsPh3) is
The first O-bridged osmium carboxylates with the
OsOOs angle significantly deviating from 180° were
heated with liquid carboxylic acids (acetic or trifluoro-
acetic acids) or with solutions of solid carboxylic acids
in benzene, dark brown diamagnetic binuclear osmium
compounds are produced with the general formula
synthesized by the authors of [10]. They showed that
the complexes with the general formula [OsI2V(µ-O)(µ-
O2CR)2X4{PPh(R')2}2] (R = CH3, C2H5; X = Cl, Br; R' =
Ph, Et) are formed when trans-[OsO2X2{PPh(R')2}2] is
refluxed in a mixture of RCO2H–(RCO)2O under the
inert atmosphere in the dark (in order to prevent the
decomposition of the starting complex). The acetate
[OsI2V(µ-O)(µ-O2CR)2ël4(L)2] (L = PPh3; R = ë(ëç3)3,
CH3, CH2Cl, CCl3, CF3, and L = AsPh3; R = CH3,
CH2Cl, CCl3, CF3). The yields of compounds increase
with the increasing electron-accepting properties of R
in carboxylic acids in the series CF3 > CCl3 > CH2Cl >
CH3 > C(CH3). The obtained compounds are stable in
air, poorly soluble in water, ethanol, ether, saturated
hydrocarbons, and limitedly soluble in acetonitrile;
they are readily soluble in chloroform, dichlo-
romethane, and benzene.
complex
[OsI2V(µ-O)(µ-O2CCH3)2Cl4(PPh3)2]
·
(C2H5)2O (I) forms suitable crystals for X-ray diffrac-
tion analysis [10].
The results obtained in [11] make it possible to con-
clude that the binuclear O-bridged osmium carboxy-
lates [OsI2V(µ-O)(µ-O2CR)2ël4(L)2] (R = CH3, L = PPh3,
X-ray diffraction analysis of [OsI2V(µ-O)(µ-
AsPh3; R = CCl3, L = PPh3) are formed in the reaction
of the corresponding trans-[OsO2Cl2L2] with carboxy- O2CCCl3)2ël4(PPh3)2] · (CH2Cl2) (II) confirms bending
lic acids under ordinary conditions (without using the of the Os2(µ-O) core. The osmium atoms are bonded by
inert atmosphere) and in the absence of (RCO)2O. The
formation, stability, and spectral properties of thus are in the trans-positions to the bridging oxygen atom
two bridging trichloroacetate ions. Two chlorine atoms
1070-3284/04/3004-0262 © 2004 åÄIä “Nauka /Interperiodica”

OSMIUM(IV) BINUCLEAR NONELECTROLYTIC OXO-BRIDGED CARBOXYLATES
263
Cl(10)
Cl(8)
Cl(6)
C(74)
O(3)
Cl(5)
C(76)
O(4)
C(75)
Cl(7)
Cl(9)
O(5)
Cl(3)
O(2)
C(73)
Os(2)
Cl(1)
P(1)
C(7)
Cl(4)
Os(1)
C(13)
O(1)
P(2)
Cl(2)
C(25)
C(1)
Fig. 1. Molecular structure of [OsI2V(µ-O)(µ-O CCCl ) ël (PPh ) ] · CH Cl .
2
3 2
4
3 2
2
2
of the Os2(µ-O). Two PPh3 molecules lie opposite to the longer. As a result, the Os···Os distance decreases,
which brings about weak Os···Os interactions.
oxygen atoms of the bridging trichloroacetate groups
(Fig. 1).
The elemental analysis and FAB mass spectroscopic
data for the isolated osmium compounds [OsI2V(µ-O)(µ-
O2CR)2ël4(L)2] (L = PPh3; R = ë(ëç3)3, CH3, CH2Cl,
CCl3, CF3, and L = AsPh3; R = CH3, CH2Cl, CCl3, CF3)
confirm that they contain the Os2(µ-O)(µ-O2CCH3)2
core. Given in Fig. 2 are the experimental and calcu-
lated [Os2O(O2CëF3)2(PPh3)2Cl2]+ fragments of FAB
The comparison of the main bond lengths and
angles in complexes II (Table 1) and I [10] indicates
that an increase in the electron-accepting properties of
R in the bridging carboxylate ligands leads to a slight
decrease in the Os–(µ-O) and Os–Cl lengths and to an
increase in the Os(µ-O)Os angle. At the same time, the
donor capability of µ-O2CCCl3 is lower than that of µ-
O2CCH3 and therefore, in complex II, the bonds Os–O
with the bridging trichloroacetate ligands become
mass
spectrum
of
the
[OsI2V(µ-O)(µ-
O2CCF3)2ël4(PPh3)2].
Table 1. Selected bond lengths (Å) and angles (deg) in [OsI2V(µ-O)(µ-O2CR)2Cl4PPh3)2]* complexes
R
R
Bond
Angle
CH3**
CCl3***
CH3**
CCl3***
Os(1)–O(1)
Os(2)–O(1)
Os(1)–Cl(1)
Os(1)–Cl(2)
1.830(10)
1.828(9)
2.306(4)
2.332(4)
1.806(11)
1.816(11)
2.278(5)
2.290(6)
Os(1)–P(1)
Os(1)–O(2)
Os(1)–O(5)
Os···Os
2.374(3)
2.118(9)
2.083(9)
3.440
2.369(6)
2.161(13)
2.101(15)
3.427
R
Angle
CH3**
CCl3***
142.2(7)
Os(µ-O)Os
140.2(4)
* The atomic numbering corresponds to that in Fig. 1.
** The data of [10].
*** The data of this work.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 4 2004

264
BELYAEV et al.
C(15)
C(16)
Relative intensity
(a)
(b)
C(14)
C(8)
C(9)
C(10)
C(11)
C(17)
C(2)
C(18)
C(1)
C(3)
C(4)
C(13)
C(7)
C(12)
Cl(1)
P(1)
C(5)
C(6)
Os(1)
Cl(2a)
Cl(2)
Cl(1a)
P(1a)
1210 1215 1220 1225 1210 1215 1220 1225
m/z
Fig.
2.
Isotopic
ionic
distribution
for
+
[Os O(O CCF ) (PPh ) Cl ] fragment (m/z 1218) in
2
2
3 2
3 2
2
[OsI2V(µ-O)(µ-O CCF ) ël (PPh ) ] complex: (a) experi-
2
3 2
4
3 2
mental, (b) calculated value.
Fig. 3. Molecular structure of trans-[Os(PPh ) Cl ].
3 2
4
The reactions of trans-[OsVIO2Cl2L2] (L = PPh3,
AsPh3) with all carboxylic acids under consideration
have low intensity and therefore, they cannot be used
for determination of the coordination mode of the
afforded the Os binuclear complexes [OsI2V(µ-O)(µ-
RCO–2 group.
O2CR)2ël4(L)2] and white crystals. The results of the
elemental analysis, IR data and the melting points indi-
cated that these crystals are triphenylphosphine oxide
(é=PPh3) or triphenylarsine oxide (é=AsPh3).
Since the starting trans-[OsVIO2Cl2(SbPh3)2] com-
plex is stable in air, one can suggest that in the reactions
of carboxylic acids with trans-[OsVIO2Cl2(SbPh3)2],
SbCl2Ph3 is likely to be eliminated due to a low stability
of an intermediate Os compound. This suggestion is
being verified now in our studies.
Thus, the formation of binuclear complexes
[OsI2V(µ-O)(µ-O2CR)2ël4(L)2] (L = PPh3, AsPh3) can be
described by the following redox reaction occurring in
solution:
When trans-[OsVIO2Cl2(PPh3)2] reacts with trimeth-
ylacetic acid, the binuclear complex [OsI2V(µ-O)(µ-
2[OsVIO2Cl2L2] + 2RCO2H
[OsI2V(µ-O)(µ-O2CR)2Cl4L2] + 2O=L + H2O,
O2CC(CH3)3)2ël4(PPh3)2] forms in less than 30% yield.
In this case, the main fraction of osmium-containing
compound accounts for the mononuclear complex
trans-[OsIV(PPh3)2Cl4]. This is confirmed by the results
of the elemental analysis and X-ray diffraction study of
this complex that forms dark brown needle-shaped
crystals. The molecular structure of trans-
[OsIV(PPh3)2Cl4] is given in Fig. 3. The trans-
L = PPh3, AsPh3.
The reactions of trans-[OsO2Cl2(SbPh3)2] with all
the studied carboxylic acids always gave SbCl2Ph3 and
the poorly soluble osmium-containing compounds of
brown color. The formation of SbCl2Ph3 was confirmed
by the elemental analysis and X-ray diffraction data [11].
The ratio Os : C in the osmium-containing products
is close to 1 : 4 for R = CH3, CH2Cl, CCl3, CF3 and to
1 : 8 for R = ë(ëç3)3. The molar ratio Os : C for all
[OsIV(PPh3)2Cl4] complex crystallizes in monoclinic
system, space group P21/n; a = 9.324(2), b = 21.022(4),
c = 9.603(2) Å, β = 117.42(3)°, V = 1670.8(6) Å3, Z =
samples under study suggests that the isolated products 2 (the main bond lengths Os(1)–Cl(1) 2.3008(16),
contain carboxylic acids. This is also confirmed by IR
data. The spectral region 1400–1600 cm–1 contains
characteristic bands that can be assigned to νas(COO) of
the carboxyl groups of the corresponding carboxylic
Os(1)–Cl(2) 2.3249(16), Os(1)–P(1) 2.5195(17) Å and
angles Cl(1a)Os(1)Cl(1) 180.0°, Cl(1a)Os(1)Cl(2)
90.89(7)°, Cl(1)Os(1)Cl(2) 89.11(7)°, Cl(1)Os(1)Cl(2a)
90.89(7)°, Cl(2)Os(1)Cl(2a) 180.00(9)°, Cl(1)Os(1)P(1a)
acids [12]. However, these bands are too broad and 92.62(6)°, Cl(2)Os(1)P(1a) 92.43(6)°, Cl(2a)Os(1)P(1a)
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OSMIUM(IV) BINUCLEAR NONELECTROLYTIC OXO-BRIDGED CARBOXYLATES
265
ε × 10–3, l mol–1 cm–1
Transmittance
20
1
2
10
0
300 400 500 600 700 800 900 1000 1100
λ, nm
Fig. 5. Electronic absorption spectra of (1)
Os O(O CCH Cl) (PPh ) Cl
and
(2)
1500
2
2
2
2
3 2
4
ν, cm–1
Os O(O CCH Cl) (AsPh ) Cl complexes in CHCl .
2
2
2
2
3 2
4
3
Fig. 4. IR spectrum of [OsI2V(µ-O)(µ-O CCF ) ël (PPh ) ]
2
3 2
4
3 2
The electronic absorption spectra typical of the
[OsI2V(µ-O)(µ-O2CR)2ël4(L)2] solutions in CHCl3 are
in the region of the stretching vibrations ν (ëéé) and
s
ν (ëéé) of the bridging carboxyl groups.
as
shown in Fig. 5. Those of the triphenylphosphine com-
plexes [OsI2V(µ-O)(µ-O2CR)2ël4(PPh3)2] in chloroform
have the absorption band at 455–458 nm. In the spectra
of the [OsI2V(µ-O)(µ-O2CR)2ël4(AsPh3)2] complexes in
ëçël3, this intense band is shifted by 20–30 nm toward
high frequencies (Fig. 5, Table 2).
87.57(6)°, Cl(1a)Os(1)P(1) 92.62(6)°, Cl(1)Os(1)P(1)
87.38(6)°).
Unfortunately, IR method provides insufficient data
in the case of binuclear Os(IV) µ-oxocarboxylates, and
an accurate assignment of the bands typical of the
stretching vibrations νs(ëéé) and νas(ëéé) of the
bridging carboxyl groups is almost impossible. The
range of 1440–1430 cm–1, where vibrations νs(ëéé)
of carboxylate ligands usually appear [12], contains
intense bands typical of the starting trans-
[OsVIO2L2Cl2] (L = PPh3, AsPh3). The bands with max-
ima at 1500–1680 cm–1 can be assigned to vibrations
νas(ëéé–) of the bridging carboxylate ions. However,
these bands have very low intensity, which is not typical
of µ-O2CR.
If the diagram of MO energy levels for the
osmium(IV) complexes with the linear configuration of
the Os–µ-O–Os core [20, 21] is applied to the binuclear
Os(IV) oxo-bridged carboxylate compounds with the
Os(µ-O)Os angle deviating from 180°, the most intense
band can be assigned then to the πnonb
inside the Os2(µ-O) core (Fig. 6).
π* transition
Table 2 contains X-ray photoelectron spectroscopy
data for the Os(IV) binuclear µ-oxocarboxylates. The
binding energies for Os 4f7/2 (52.7–53.1 eV) and Cl
2p3/2 (198.6–199.0 eV) correlate with the data of [10,
21] and correspond to the formal oxidation state of
osmium +4. The changes in X-ray photoelectron spec-
tra do not make it possible to establish any general reg-
IR spectrum of [OsI2V(µ-O)(µ-O2CCF3)2ël4(PPh3)2]
(Fig. 4) exhibits a relatively intense band at 1622 cm–1
that is likely to be due to vibrations νas(ëéé) of the
bridging trifluoroacetate groups. The comparison of ularities and only reflect the result of the competing
this band with the band corresponding to νas(ëéé) of donation of the electron density of ligands L, chloride
anions, and the bridging carboxylate groups.
the bridging acetate groups in [OsI2V(µ-O)(µ-
O2CCH3)2ël4(PPh3)2] (observed by us at 1530 cm–1 and
at 1540–1525 cm–1 in [10]) revealed the general ten-
dency of shifting of the respective frequency in the tri-
fluoroacetate complexes toward high-frequency region.
The latter fact is characteristic of the bi- and trinuclear
O-bridged trifluoroacetate complexes of Cr [13], Ru
[14–16], and Rh [17–19].
EXPERIMENTAL
The starting trans-OsO2Cl2(PPh3)2 was prepared as
described elsewhere [22], while trans-OsO2Cl2L2 and
[OsI2V(µ-O)(µ-O2CCH3)2Cl4L2] (L = AsPh3, SbPh3) we
obtained using procedures [11].
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266
BELYAEV et al.
Table 2. X-ray photoelectron and electronic absorption spectra of Os µ-oxocarboxylates [OsI2V(µ-O)(µ-O2CR)2Cl4(L)2]
Electronic
X-ray photoelectron spectra**, eV
absorption spectra*
L
R
λmax, nm
Os 4f7/2
P 2p3/2
As 3d
Cl 2p3/2
(ε, l mol–1 cm–1)
PPh3
C(CH3)3
CH3
456 (10300)
456 (10100)
458 (17300)
455 (13600)
455 (10400)
426 (7400)
52.7
52.8
53.1
53.0
52.6
52.9
53.0
52.8
52.8
132.3
133.4
132.3
132.6
132.0
198.6
199.0
199.3
198.8
199.0
198.9
199.0
198.6
198.8
CH2Cl
CCl3
CF3
AsPh3
CH3
44.6
44.5
44.6
44.6
CH2Cl
CCl3
CF3
434 (11500)
426 (11400)
425 (12000)
* The spectra were recorded in chloroform.
** The spectra are normalized in terms of the binding energy of electrons of the C1s line taken as 285.0 eV.
Synthesis
of
[OsI2V(m-O){m-
stituted hydrocarbons or arenes.
O2CC(CH3)3}2Cl4(PPh3)2]. A suspension of trans-
[OsO2(PPh3)2Cl2] (1 g) in 20 ml of C(CH3)3CO2H (4 g)
in chloroform was heated with reflux condenser until
the starting complex dissolved completely. After the
unreacted trans-[OsVIO2(PPh3)2Cl2] was filtered off,
the excess solvent was distilled off from the reaction
mixture, whereas pivalic acid excess was removed by
sublimation. The remaining solid was dissolved in
chloroform and the targeted product was salted out with
hexane. The complex was dried in a vacuum desiccator
over potassium hydroxide. The yield was ~30%. The
complex is insoluble in water, alcohols, limitedly solu-
ble in acetonitrile, and readily soluble in halogen-sub-
For C46H48Cl4O5Os2P2
anal. calcd. (%): Os, 19.04;
C, 43.27;
C, 43.5;
Cl, 7.10.
Cl, 8.0.
Found (%):
Os, 18.9;
FAB (m/z): 1231 [M–Cl]+. IR (ν, cm–1): 443 w, 553 s,
619 w, 691 s, 744 m, 997 w, 1028 w, 1092 m, 1159 w,
1220 w, 1408 w, 1435 s, 1482 m, 1698 m, 2927 w,
2965 w, 3059 w, 3440 b.
Synthesis of [Os2IV(m-O)(m-O2CCH2Cl)2Cl4(PPh3)2].
A suspension of [OsO2(PPh3)2Cl2] (1.5 g) in 20 ml of
CH2ClCO2H (5 g) in chloroform was heated with reflux
condenser until the starting complex dissolved. The
excess solvent was distilled off from the reaction mix-
ture; the remaining solid containing the complex and
monochloroacetic acid was suspended in cold water.
This aqueous solution was decanted and this procedure
was repeated to get neutral reaction of washing water.
The complex was filtered off and dired in a vacuum des-
iccator over silica gel to a constant weight. The com-
plex yield was ~90%.
y
x
*
π2
*
π1
z
π‡2ÌÚË
π1‡ÌÚË
dyz,
dxz,
dxy
dxy
px, py
For C40H34Cl6O5Os2P2
anal. calcd. (%): Os, 30.44;
Found (%): Os, 38.2;
C, 38.44;
C, 39.2;
Cl, 17.01.
Cl, 16.3.
π2
π1
O2–
2 Os(IV)
OsIV–O2––OsIV
FAB (m/z): 1215 [M–Cl]+. IR (ν, cm–1): 524 s, 691 s,
747 m, 798 w,997 w, 1094 m, 1121 m, 1191 s, 1258 m,
1399 m, 1433 m, 1483 w, 1561 s, 2924 w, 3058 w, 3442 b.
Fig. 6. Energy levels of MO for Os(IV) O-bridged carbox-
ylate complexes.
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OSMIUM(IV) BINUCLEAR NONELECTROLYTIC OXO-BRIDGED CARBOXYLATES
267
Synthesis of [Os2IV(m-O)(m-O2CCCl3)2Cl4(PPh3)2] as the [OsI2V(µ-O)(µ-O2CCF3)2Cl4(PPh3)2] complex. The
was carried out similarly to that of [OsI2V(µ-O)(µ-
dark brown complex was obtained in the yield of ~70%.
O2CCH2Cl)2Cl4(PPh3)2]. The yield was ~95%.
For C40H36O5As2Cl4Os2
anal. calcd. (%):
Found (%):
Os, 30.0;
Os, 29.8;
Cl, 11.2.
Cl, 11.4.
For C40H30Cl10O5Os2P2
anal. calcd. (%): Os, 27.42;
C, 34.62;
C, 35.2;
Cl, 25.55.
Cl, 24.6.
Found (%):
Os, 26.9;
FAB (m/z): 1235 [M–Cl]+. IR (ν, cm–1): 472 s, 690 s,
740 s, 778 w, 850 b, 1000 w, 1028 w, 1085 s, 1163 b,
1187 b, 1440 s, 1490 w, 1630 s, 3420 b.
FAB (m/z): 1351 [M–Cl]+. IR (ν, cm–1): 518 w, 610 b,
682 s, 718 w, 743 s, 820 w, 847 m, 1340 w, 1430 w,
1500 w, 1605 w.
The needle-shaped crystals are formed on slow
evaporation of the complex solution in methylene chlo-
ride. The complex cocrystallizes with one CH2Cl2 mol-
[OsI2V(m-O)(m-O2CCH2Cl)2Cl4(AsPh3)2] was syn-
thesized using the same procedure as in the case of the
[OsI2V(µ-O)(µ-O2CCH2Cl)2Cl4(PPh3)2] complex. The
yield was ~75%.
ecule. The crystals are triclinic, space group P1 ; a =
10.747(2) Å, b = 19.291(4) Å, c = 24.614(5) Å, α =
100.08(3)°, β = 90.63(3)°, γ = 97.05(3)°, V =
4983.5(17) Å3, Z = 4.
For C40H34As2Cl6O5Os2
anal. calcd. (%): Os, 28.44;
Found (%): Os, 27.8;
C, 35.91;
C, 36.6;
Cl, 15.90.
Cl, 14.3.
Synthesis of [OsI2V (m-O)(m-O2CCF3)2Cl4(PPh3)2].
FAB (m/z): 1303 [M–Cl]+. IR (ν, cm–1): 471 m,
544 w, 691 s, 739 s, 810 m, 841 m, 997 w, 1025 w,
1082 m, 1188 m, 1258 m, 1311 m, 1397 s, 1438 vs,
1481 m, 1561 m, 2854 w, 2925 w, 3055 w, 3442 b.
[OsI2V(m-O)(m-O2CCCl3)2Cl4(AsPh3)2] was synthe-
sized similarly to that of [OsI2V(µ-O)(µ-
O2CCH2Cl)2Cl4(PPh3)2]. The yield of the complex was
~90%.
A sample of trans-[OsO2Cl2(PPh3)2] (1 g) was boiled
with excess CF3CO2H (20 ml) in a flask with reflux con-
denser for 2 h. The excess solvent was distilled off, and
the dry residue was dissolved in chloroform. The target
product was precipitated with hexane. The complex
was dried in a vacuum desiccator over KOH to a con-
stant weight. The obtained dark brown compound is
insoluble in water or alcohol; limitedly soluble in ace-
tone, and readily soluble in ether, chloroform, or ben-
zene. The yield was ~80%.
For C40H30As2Cl10O5Os2
For C40H30Cl4F6O5Os2P2
anal. calcd. (%): Os, 25.79;
Found (%): Os, 25.3;
C, 32.56;
C, 31.8;
Cl, 24.03.
Cl, 22.4.
anal. calcd. (%): Os, 29.52;
Found (%): Os, 29.3;
C, 37.28;
C, 37.8;
Cl, 11.00.
Cl, 12.2.
FAB (m/z): 1439 [M–Cl]+. IR (ν, cm–1): 471 m,
687 vs, 741 vs, 845 m, 998 w, 1025 w, 1082 w, 1188 w,
1274 m, 1343 m, 1437 s, 1481 w, 1617 w, 2855 w,
2924 w, 3055 w, 3441 b.
FAB (m/z): 1255 [M–Cl]+, 1177 [M–O2CCF3]+. IR
(ν, cm–1): 432 m, 523 s, 691 s, 731 m, 860 w, 999 w,
1094 m, 1153 m, 1196 s, 1385 w, 1436 m, 1485 w,
1622 m, 2854 w, 2925 w, 3059 w, 3440 b.
Synthesis of [OsI2V(m-O)(m-O2CCF3)2Cl4(AsPh3)2]
Synthesis
of
[OsI2V(m-O){m-
was carried out using the same procedure as in the case
O2CC(CH3)3}2Cl4(AsPh3)2] was performed similarly
of [OsI2V(µ-O)(µ-O2CCF3)2Cl4(PPh3)2]. The complex
was obtained in ~(60–70)% yield.
to that of [OsI2V(µ-O){µ-O2CC(CH3)3}2Cl4(PPh3)2].
The yield of dark brown complex was ~50%.
For C40H30As2Cl4F6O5Os2
For C46H48As2Cl4O5Os2
anal. calcd. (%): Os, 27.63;
Found (%): Os, 26.9;
C, 34.90;
C, 35.2;
Cl, 10.30.
Cl, 9.3.
anal. calcd. (%):
Found (%):
Os, 28.12;
Os, 27.6;
Cl, 10.48.
Cl, 9.8.
FAB (m/z): 1343 [M–Cl]+. IR (ν, cm–1): 471 m,
620 w, 690 s, 737 s, 789 w, 839 w, 1082 m, 1196 vs,
1388 w, 1437 m, 1481 w, 1625 m, 2924 w, 3057 w,
3449 b.
FAB (m/z): 1318 [M–Cl]+. IR (ν, cm–1): 472 s,
690 s, 740 s, 778 w, 850 b, 1000 w, 1028 w, 1085 s,
1163 b, 1187 b, 1440 s, 1490 w, 1630 s, 3420 b.
Synthesis of [OsI2V(m-O)(m-O2CCH3)2Cl4(AsPh3)2].
The electronic absorption spectra of solutions of the
This complex was synthesized by the same procedure complexes were recorded on a SF-56 spectrophotome-
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 4 2004

268
BELYAEV et al.
4. Knopp, P. and Wieghardt, K., Inorg. Chem., 1991,
ter in the range of 190–1100 nm in quartz cells with l =
1 cm. IR spectra in the range of 4000–400 cm–1 were
taken on a Nicolet FT-360 spectrophotometer (with
KBr pellets); FAB mass spectra were recorded on a
Trio2000 mass spectrometer in the region of positively
charged ions by bombarding 3-nitrobenzyl alcohol
matrices with xenon atoms.
vol. 30, no. 21, p. 4061.
5. Tanase, T. and Lippard, S.J., Inorg. Chem., 1995, vol. 34,
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Inorg. Chem., 1999, vol. 38, no. 1, p. 190.
X-ray photoelectron spectra were measured on a
Perkin-Elmer PHI 5400 electron spectrophotometer
with MgKα source. The powdered samples were pressed
in indium and after preliminary evacuation were placed
on a manupulator cooled with liquid nitrogen. The work-
ing vacuum in spectrometer was 10–8 mmHg.
8. Tanase, T., Takeshita, N., Inoue, C., et al., J. Chem. Soc.,
Dalton Trans., 2001, no. 15, p. 2293.
9. Abe, M., Mitani, A., Ohsawa, A., et al., Inorg. Chim.
Acta, 2002, vol. 331, p. 158.
10. Armstrong, J.E., Robinson, W.R., and Walton, R.A.,
Inorg. Chem., 1983, vol. 22, no. 9, p. 1301.
1
X-ray diffraction analysis was carried out on a
11. Belyaev, A.N., Eremin, A.V., Simanova, S.A., et al., Zh.
Prikl. Khim. (S.-Peterburg), 2002, vol. 75, no. 12,
p. 1947.
12. Nakomoto, K., Infrared and Raman Spectra of Inorganic
and Coordination Compounds, Chichester: Wiley, 1986.
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Prikl. Khim. (S.-Peterburg), 1998, vol. 71, no. 9, p. 1417.
14. Neubold, P., Wieghardt, K., Nuber, B., et al., Inorg.
Chem., 1989, vol. 28, no. 3, p. 459.
four-circle automated Syntex P21 diffractometer. The
elemental analysis of the complexes for C was per-
formed on a Perkin-Elmer 2400 CHN analyzer; Os was
determined gravimetrically after the complexes were
reduced in a flow of hydrogen; Cl was found by poten-
tiometrical titration with silver ions of solutions of
cakes of the complexes with excess potassium carbon-
ate in a 10% nitric acid.
15. Belyaev, A.N., Simanova, S.A., Eremin, A.V., et al., Zh.
Prikl. Khim. (S.-Peterburg), 1995, vol. 68, no. 1, p. 76.
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p. 1975.
Peaks of molecular masses were calculated using
polynomial expansion based on the natural isotope
abundance with IsoPro [23] and Molecular Weight Cal-
culator [24] programs.
17. Belyaev,A.N., Simanova, S.A., Gorlov, M.Yu., et al., Zh.
Prikl. Khim.(S.-Peterburg), 1998, vol. 71, no. 12,
p. 1971.
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Prikl. Khim.(S.-Peterburg), 2000, vol. 73, no. 11,
p. 1778.
ACKNOWLEDGMENTS
This work was supported by the Russian Foundation
for Basic Research (project no. 02-5.0-263).
19. Belyaev,A.N., Simanova, S.A., Gorlov, M.Yu., et al., Zh.
Obshch. Khim., 2000, vol. 71, no. 8, p. 1259.
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1
The study was performed in the Karpov Institute of Physical
Chemistry (State Research Center of the Russian Federation,
Moscow).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 30 No. 4 2004