Synthesis and molecular structures of tris(thio- and selenophenyl)stannyl complexes of cyclopentadienylcarbonylnitrosylmanganese and their reaction products with tungsten carbony

Article abstract of DOI:10.1134/S1070328411110108

Reactions of CpMn(CO)(NO)SnCl₃ (I) with sodium benzenethiolate and sodium benzenesele-nolate gave orange crystals of the complexes CpMn(CO)(NO)Sn(EPh)₃, where E = S (II) or Se (III). Treatment of complex II with photochemically generated W(CO)₅(THF) yielded the adduct CpMn(CO)(NO)Sn(SPh)₃ ? W(CO)₅ (IV). A similar treatment of complex III resulted in the formation of the ditungsten complex W₂(CO)₄(SePh)₆ (V) with transfer of all chalcogenate groups from tin to tungsten. In reactions of complexes II and III with a Pt₀ complex with phosphine and acetylene, (PPh ₃)₂Pt(Ph₂C₂), the chalcogenate groups are transferred from tin. Only the known Pt(II) complexes (PPh ₃)₂Pt(EPh)₂), where E= S (VI) or Se (VII). Molecular structures IV and V were characterized by X-ray diffraction. It has been found that the Mn-Sn bond in complex IV (2.5479(9) A) is nearly the same length as that found earlier for complex II (2.5328(17) A) and is substantially shorter than the sum of the covalent radii of Mn and Sn (2.78 A). The Sn-S bond is noticeably lengthened (2.5217(11) A) only for the S atom bound to tungsten (W-S, 2.5696(12) A), while the other Sn-S bonds (2.4413(12) and 2.4291(12) A) are virtually the same as in complex II (on average, 2.441 A). Complex V contains the direct W-W bond (2.8153(16) A) supplemented with four benzeneselenolate bridges in which the W-Se bonds (on average, 2.642(2) A) are longer than the two terminal W-SePh bonds (2.571(2) A). All the W-Se bonds are much shorter than the sum of the covalent radii of W and Se (2.82 A).

Full text of DOI:10.1134/S1070328411110108

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2011, Vol. 37, No. 12, pp. 879–886. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.A. Pasynskii, A.I. Blokhin, Yu.V. Torubaev, Zh.V. Dobrokhotova, 2011, published in Koordinatsionnaya Khimiya, 2011, Vol. 37, No. 12, pp. 883–890.
Synthesis and Molecular Structures of Tris(thioꢀ
and Selenophenyl)stannyl Complexes
of Cyclopentadienylcarbonylnitrosylmanganese
and Their Reaction Products with Tungsten Carbonyl
A. A. Pasynskii*, A. I. Blokhin, Yu. V. Torubaev, and Zh. V. Dobrokhotova
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
*eꢀmail: aapas@rambler.ru
Received April 15, 2011
Abstract—Reactions of CpMn(CO)(NO)SnCl3 (I) with sodium benzenethiolate and sodium benzeneseleꢀ
nolate gave orange crystals of the complexes CpMn(CO)(NO)Sn(EPh)3, where E = S (II) or Se (III). Treatꢀ
ment of complex II with photochemically generated W(CO)5(THF) yielded the adduct
CpMn(CO)(NO)Sn(SPh)3
ditungsten complex W2(CO)4(SePh)6
reactions of complexes II and III with a Pt0 complex with phosphine and acetylene, (PPh3)2Pt(Ph2C2), the
chalcogenate groups are transferred from tin. Only the known Pt(II) complexes (PPh3)2Pt(EPh)2), where
E = S (VI) or Se (VII). Molecular structures IV and were characterized by Xꢀray diffraction. It has been
⋅
W(CO)5
(
IV). A similar treatment of complex III resulted in the formation of the
(V
) with transfer of all chalcogenate groups from tin to tungsten. In
V
found that the Mn–Sn bond in complex IV (2.5479(9) Å) is nearly the same length as that found earlier for
complex II (2.5328(17) Å) and is substantially shorter than the sum of the covalent radii of Mn and
Sn (2.78 Å). The Sn–S bond is noticeably lengthened (2.5217(11) Å) only for the S atom bound to tungsten
(W–S, 2.5696(12) Å), while the other Sn–S bonds (2.4413(12) and 2.4291(12) Å) are virtually the same as in
complex II (on average, 2.441 Å). Complex
V contains the direct W–W bond (2.8153(16) Å) supplemented
with four benzeneselenolate bridges in which the W–Se bonds (on average, 2.642(2) Å) are longer than the
two terminal W–SePh bonds (2.571(2) Å). All the W–Se bonds are much shorter than the sum of the covalent
radii of W and Se (2.82 Å).
DOI: 10.1134/S1070328411110108
Among a variety of complexes containing transiꢀ argon in dehydrated solvents. Complex
I and
tion metal–tin bonds [1], the carbonylcyclopentadieꢀ PPh3)2Pt(PhC CPh) were prepared as described in
(
≡
nylnitrosylstannylmanganese complexes CpMn(CO) [3] and [5], respectively. Silica gel for column chromaꢀ
(NO)SnХ3 [2, 3] are of interest because of the chirality tography was heated in vacuo at 100°C for 1 h for
removal any air and moisture. IR spectra were
recorded on a Specord 75 IR spectrophotometer (KBr
pellets).
of the Mn atom surrounded by four different ligands
(including the partially double Mn–Sn bond). This
bond is shorter by 0.3 Å than the sum of the covalent
radii of the corresponding metal atoms (2.78 Å [4]) and
only slightly depends on the substituents X at the tin
Synthesis of complex II. Sodium borohydride
(0.025 g, 0.66 mmol) was added to a stirred solution of
Ph2S2 (0.07 g, 0.33 mmol) in ethanol (10 mL). After
1 h, solidꢀstate СрMn(CO)(NO)SnCl3 (0.09 g,
0.2 mmol) was added to the resulting transparent soluꢀ
tion of sodium benzenethiolate. The solution turned
dark yellow, immediately producing a white precipiꢀ
tate. The reaction mixture was stirred for 1 h and evapꢀ
orated to dryness in a water aspirator vacuum. The yelꢀ
low residue was subjected to extraction with CH2Cl2
(10 mL) and the organic extract was filtered. TLC
atom (X = Cl (
have obtained complex II from sodium benzenethiolate
I
), SPh (II) [2], or
C
≡
CPh [3]). Earlier, we
+
−
and the ionic complex
[2].
CpMn CO NO SnCl3
)2 (
(
)
Here we describe the synthesis of complex II and its seleꢀ
nium analog CpMn(CO)(NO)Sn(SеPh)3 (III directly
from covalent complex , as well as reactions of comꢀ
)
I
plexes II and III with tungsten and platinum comꢀ
plexes.
data: yellow spot, Rf 0.44, CH2Cl2–light petroleum
(2 : 1). The mother liquor was diluted with light petroꢀ
leum (10 mL) and the resulting solution was concenꢀ
EXPERIMENTAL
All manipulations dealing with the synthesis and trated in vacuo until crystallization began and then
isolation of the complexes were carried out under kept at –5 for 24 h. The orange needleꢀlike crystals
°С
879

880
PASYNSKII et al.
that formed were separated from the mother liquor
and dried. The yield of complex II was 0.07 g (47.6%). 1875 s (
IR (KBr,
ν
, cm–1): 2055 m, 2015 m, 1980 m, 1925 s,
(CO)), 1780 s ( (NO)), 835 s, 1015 m
ν
ν
(C5H5).
For C24H20NO2S3MnSn
anal. calcd., %: C, 42.34; H, 3.13; N, 1.98; S, 13.56.
Found, %: C, 42.89; H, 2.85; N, 2.29; S, 13.29.
⋅
CH2Cl2 (Mr 709.17).
Synthesis of complex V. Pentacarbonyltetrahydroꢀ
furantungsten (0.23 g, 0.65 mmol) was added dropwise
at –5 C for 20 min to a stirred yellow solution of comꢀ
°
plex III (0.5 g, 0.65 mmol) in THF (20 mL). The
resulting brown solution was concentrated in vacuo for
1 h. The brown residue was dissolved in CH2Cl2
IR (KBr, ν, cm–1): 2000 s (
1005 m (C5H5), 835 m.
1H NMR (CDCl3
, , ppm): 7.61, 7.59, 7.25, 7.22,
ν
(CO)), 1760 s ( (NO)),
ν
(15 mL). TLC data: brown spot, Rf 0.43, CH2Cl2–hexꢀ
δ
ane (1 : 1). The product was isolated by column chroꢀ
matography (column height 15 cm, column diameter
2.5 cm) on silica gel with preliminary elution of
7.20 s (17H), 4.43 s (5H).
Synthesis of complex III. Sodium borohydride
(0.04 g, 1.2 mmol) was added to a stirred yellow soluꢀ
tion of Ph2Se2 (0.17 g, 0.6 mmol) in ethanol (10 mL).
After 10 min, solidꢀstate СрMn(CO)(NO)SnCl3
(0.15 g, 0.2 mmol) was added to the resulting transparꢀ
ent solution of sodium benzeneselenolate. The soluꢀ
tion turned dark yellow, immediately producing a
white precipitate. The reaction mixture was stirred for
1 h and concentrated in vacuo. The yellow residue was
subjected to extraction with CH2Cl2 (10 mL). TLC
W(CO)6 and impurities with heptane and CH2Cl2
–
heptane (40 mL). The brown reaction product was
eluted with CH2Cl2 (40 mL) and left for crystallization
in a mixture of CH2Cl2 (15 mL) and heptane (1 mL) at
–5
that formed were separated from the mother liquor
and dried. The yield of complex was 0.51 g (52%).
°
С for 24 h. The brown hexagonal prismatic crystals
V
For C40H30O4Se6W2
anal. calcd., %:
Found, %:
⋅
CH2Cl2 (Mr 1501.07)
data: yellow spot, Rf 0.52, CH2Cl2–hexane (2 : 1). The
C, 32.81;
C, 32.93;
H, 2.15.
H, 2.19.
product was isolated by column chromatography (colꢀ
umn height 5 cm, column diameter 2 cm) on silica gel
with preliminary elution of the unreacted Ph2Se2 with
hexane and CH2Cl2–hexane (40 mL). The dark yellow
reaction product was eluted with CH2Cl2 (40 mL). The
eluate was evaporated to dryness and the residue was
dissolved in hot hexane (15 mL). The resulting soluꢀ
IR (KBr,
ν
, cm–1): 1985 s, 1935 s (
ν
(CO)), 1010 m
(Ph), 840 m.
Synthesis of complex VI. A colorless solution of
PPh3)2Pt(PhC CPh) (0.14 g, 0.16 mmol) in THF
(
≡
tion was left at room temperature for 2 h. The dark yelꢀ (10 mL) was added to a stirred yellow solution of comꢀ
low needleꢀlike crystals that formed were separated plex II (0.1 g, 0.16 mmol) in THF (15 mL). The reacꢀ
from the mother liquor and dried in a water aspirator tion mixture was stirred for 1 h, producing a beige preꢀ
vacuum. The yield of complex III was 0.08 g (45%).
cipitate. The solvent was removed in vacuo and the
yellow residue was dissolved in diethyl ether (15 mL).
The resulting solution was filtered and diluted with
For C24H20NO2Se3MnSn (
M
r 764.94)
H, 2.64;
H, 1.87;
anal. calcd., %:
Found, %:
C, 37.68;
C, 38.69;
N, 1.83.
N, 1.62.
heptane (5 mL). TLC data: yellow spot, Rf 0.53
diethyl ether–heptane (1 : 1). The solution was kept at
–5 for 24 h. The yellow tetragonal prismatic crystals
,
°С
that formed were separated from the mother liquor
and dried. The yield of complex VI was 0.08 g (49%).
IR (CH2Cl2
,
ν, cm–1): 1990 s (
ν
(CO)), 1755 s
(
ν
(NO)).
Synthesis of complex IV. Pentacarbonyltetrahydroꢀ
furantungsten (0.28 g, 0.80 mmol) was added dropwise
at to a stirred yellow solution of complex II (0.5 g,
For C48H40P2S2Pt (Mr 937.99)
anal. calcd., %: C, 61.46;
H, 4.30;
H, 3.89;
S, 6.84.
S, 6.82.
0°С
Found, %:
IR (KBr,
C, 61.28;
0.80 mmol) in THF (40 mL). After the addition was
completed, the resulting dark red solution was stirred
for 1 h and concentrated in vacuo. The red residue was
subjected to extraction with heptane (90 mL). TLC
data: orange spot, Rf 0.47, CH2Cl2–heptane (1 : 1).
The extract was concentrated in vacuo until crystalliꢀ
ν
, cm–1): 740 s, 690 m (Ph).
Complex VII was obtained from complex III (0.1 g,
0.13 mmol) and (PPh3)2Pt(PhC CPh) (0.12 g,
≡
0.13 mmol) as described above for the synthesis of
complex VI. The yield of complex VII was 0.07 g
(52%).
zation began and then kept at –5 С for 24 h. The red
°
prismatic crystals that formed were separated from the
mother liquor and dried in vacuo. The yield of comꢀ
plex IV was 0.17 g (23.7%).
For C48H40P2Se2Pt (
anal. calcd., %:
Found, %:
M
r 1031.79).
C, 55.88;
C, 55.81;
H, 3.91.
H, 3.79.
For C29H20NO7S3MnSnW (
anal. calcd., %: C, 36.74; H, 2.13; N, 1.48; S, 10.14.
Found, %: C, 36.80; H, 2.36; N, 2.53; S, 10.57.
Mr 948.14)
IR (KBr,
, cm–1): 740 s, 685 m (Ph).
ν
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
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2011

SYNTHESIS AND MOLECULAR STRUCTURES
881
Mn(1)
O(1)
C(1)
N(1)
Sn(1)
S(1)
O(2)
S(2)
O(6)
S(3)
O(3)
C(6)
C(3)
C(5)
W(1)
O(5)
C(4)
O(4)
C(7)
O(7)
Fig. 1. Molecular structure of complex IV. Selected bond lengths: Sn(1)–Mn(1), 2.548(2) Å; W(1)–S(3), 2.568(3) Å;
Sn(1) S(1), 2.443(3) Å; Sn(1)–S(2), 2.429(3) Å; Sn(1)–S(3), 2.521(3) Å.
⎯
(а)
(b)
(c)
0.4
0.2
110
100
90
0
0
–1
–0.2
80
–0.4
–0.6
–0.8
–1
70
–2
–3
–4
60
50
–1.2
–1.4
40
30
–5
50 70 90 110 130 150 170 190 210
T,°C
50
150 250 350 450
T
50
150 250 350 450
,°C
T,°C
Fig. 2. Complex IV: plots of (a) the heat flux and (b) the weight vs. the temperature in the 50–450°C range and (c) the DTG curve
in the 50–200°C range.
Xꢀray diffraction analysis. Crystallographic paramꢀ tively. The atomic coordinates and other parameters of
structures IV and
V have been deposited with the
eters and the data collection and refinement statistics
for structures IV and are given in table. Structures IV
and were solved by the direct methods and refined
anisotropically (isotropically for the H atoms) by the
leastꢀsquares method on F2 with the SHELXTL proꢀ
gram package [6]. The hydrogen atoms were located
geometrically. Selected bond lengths in structures IV
Cambridge Crystallographic Data Collection
V
(nos. 814823 (IV) and 814824 (V); http://www.
ccdc.cam. ac.uk/data_request/cif).
V
The thermolysis of complex IV was examined by
DSC and TGA on NETZSCH instruments. TG meaꢀ
surements were carried out under argon (flow rate
and V are given in the captions to Figs. 1 and 2, respecꢀ 20 mL/min; Ar > 99.998%, O2 < 0.0002%, N2 <
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
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882
PASYNSKII et al.
Crystallographic parameters and the data collection and refinement statistics for structures IV and
V
Value
Parameter
IV
V
M
948.12
1416.10
Diffractometer
Bruker APEX II CCD
Mo (0.71073)
Radiation (
, K
λ, Å)
K
α
T
296(2)
Crystal system
Space group
Triclinic
Orthorhombic
Pbca
P1
a
, Å
, Å
10.863(3)
11.495(3)
15.438(3)
98.457(3)
103.538(3)
115.882(3)
1616.3(7)
2
18.5701(9)
10.9872(5)
25.9794(13)
90
b
c
, Å
, deg
, deg
, deg
α
β
90
γ
90
V
Z
, Å3
5300.7(4)
4
ρcalcd, g/cm3
1.948
1.774
μ
F
θ
, mm–1
4.939
8.487
(000)
908
2616
scan range
ω
, deg
2.05–29.00
2.19–29.00
Ranges of
h
,
k
, and
l
indices
–14 <
–15 <
h
k
< 14,
< 15,
< 21
0 <
0 <
h
k
< 25,
< 14,
< 35
–20 <
l
0 < l
Scan mode
Number of independent reflections (N1
Number of reflections with > 2( ) (N2
Number of parameters refined
GOOF (F2
1 for N2
wR2 for N1
Δρmax Δρmin
ω
)
)
8557
5771
7003
5377
I
I
388
235
)
0.918
1.022
R
0.0374
0.0610
1.032/–0.760
0.0351
0.0788
1.874–0.981
/
, e
Å–3
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
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SYNTHESIS AND MOLECULAR STRUCTURES
883
0.001%, water vapor < 0.0003%, СН4 < 0.0001%) in action of the
alundum crucibles on a TG 209 F1 instrument; the vacant orbitals of tin rather than with the antibondꢀ
orbitals of the Sn–X bonds.
A similar reaction of complex
d electrons of manganese with the
d
heating rates were 3, 5, and 10°C/min. The weights of ing
samples were 0.5 to 3 mg. DSC experiments were carꢀ
σ
*
I
with three equivaꢀ
ried out under argon on a DSC 204 F1 calorimeter in
aluminum cells at a heating rate of 10°C/min. The
weights of samples were 1 to 4 mg. The thermobalance
and the calorimeter were temperature calibrated using
the phase transition points of certified standards
lents of NaSePh in ethanol gave complex III
(Scheme 2) as orange needleꢀlike crystals that are also
soluble in nonpolar solvents and are gradually hydroꢀ
lyzed in air:
(
C6H12, Hg, KNO3, In, Sn, Bi, and CsCl; 99.99%
purity) in compliance with the norm ISO/CD 11357ꢀ1.
Samples for TG and DSC experiments were weighed
on a SARTORIUS RESEARCH R 160P analytical
balance with an accuracy of 0.01 mg. TG and DSC
data were processed according to the standards ISO
11357ꢀ1, ISO 11357ꢀ2, ISO 11358, and ASTM E
1269ꢀ95 with the NETZSCH Proteus Thermal Analꢀ
ysis software.
NaSePh
C2H5OH
Mn
Mn
SnCl3
Sn(SePh)3
CO
CO
NO
(I)
NO
(III)
Xꢀray powder diffraction analysis of the thermolyꢀ
sis products was carried out on a Guinier G670 camera
Scheme 2.
(HUBER, CuK 1 radiation).
α
Complex III was characterized by elemental analꢀ
ysis and IR spectroscopy. We failed to grow its crystals
suitable for Xꢀray diffraction. The absorption bands of
the CO and NO stretching vibrations in complex III
(1995 and 1765 cm–1, respectively) are similar to those
RESULTS AND DISCUSSION
Complex instantaneously reacts with sodium
I
benzenethiolate; the reaction is accompanied by a
color change and the formation of a white precipitate
(Scheme 1). Complex II was isolated as orange neeꢀ
dleꢀlike crystals that are soluble in nonpolar solvents
and are gradually hydrolyzed in air. The IR spectra and
elemental analysis data for complex II are identical
with those cited in [2]; however, its yield (47%) was
twice as high. The frequencies of the ν(CO) and
ν(NO) vibrations in complex II (1995 and 1765 cm–1,
respectively) are virtually identical with those found
in the spectrum of complex II
.
In a reaction of complex
I
with NaTePh, the reacꢀ
tion product was detected in the reaction mixture by
IR spectroscopy; however, attempted isolation
resulted in its decomposition.
The presence of the lone electron pair at the S
atoms in complex II allows its reaction with pentacarꢀ
bonyltetrahydrofurantungsten, yielding adduct IV
(Scheme 3):
for the complex CpMn(CO)(NO)Sn(C CPh)3 (2000
≡
and 1765 cm–1, respectively) [3].
Ph
W(CO) THF
5
:
S
[SPh]–
EtOH
Cl
THF
W(CO)5
S
Ph
Mn
Mn
NO
Sn
Sn(SPh)3
:
S
Mn Sn Cl
Mn Sn
CO
CO
SPh
NO
(II)
Cl
SPh
:
S
NO
CO
CO
NO
Ph
(IV)
(II)
(I)
Scheme 3.
Scheme 1.
Like the starting complex II, red complex IV is well
Thus, the fragment Sn(SPh)3 is comparable soluble in nonpolar solvents (e.g., hexane) and thus
with Sn(C CPh)3 in donor acceptor properties. can easily be isolated. Structure IV was characterized
≡
⎯
Therefore, it is no wonder that the Mn–Sn bond in by elemental analysis, IR spectroscopy, and Xꢀray difꢀ
complex II is shorter (2.5328(17) Å) than the sum of fraction (Fig. 1, table). The IR spectrum of
the covalent radii of these metals (2.78 Å). The single complex IV shows the increasing frequencies of the
Sn–S bonds (on average, 2.441 Å) do not exceed the CO and NO stretching vibrations at the Mn atom to
sum of the covalent radii (2.44 Å). Following [7], one 2015 and 1780 cm–1, respectively, which is due to the
can assume that the shortening of the formally single coordination of the S atom to the electronꢀwithdrawꢀ
Mn⎯Sn bonds results from an additional dative interꢀ ing pentacarbonyltungsten. In structure IV, this leads
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
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884
PASYNSKII et al.
only to the lengthening of the corresponding Sn–S and manganese. The further weight loss
bond (2.5217(11) Å) compared to the other two Sn–S
.5% in a range from 125 to 145°C (before the exoꢀ
bonds (2.4413(12) and 2.4291(12) Å), the Mn–Sn thermic effect) is due to elimination of the remaining
Δ
m = 12.5
1
bond remaining virtually intact (2.5479(9) Å). Note
that the formally single W–S bond (2.5696(12) Å) is
also noticeably shorter than the sum of the covalent
radii of these elements (2.67 Å), probably because of
three CO groups and one NO group coordinated to
manganese. Another endothermic peak at 152–270
=18.0 .5%) can be attributed to elimination of
Ph2S2 and structural rearrangement. Finally, a diffuse
endothermic peak appears at 270–400 C ( = 20.6
°
С
(
Δ
m
1
an additional W
→
S opposite bond. At the same time,
°
Δ
m
1.5%). This weight loss corresponds to elimination of
the phenyl and cyclopentadienyl fragments, which
leaves an Xꢀray amorphous solid of the formula
MnSnSW (its mass is 41.5% of the starting
complex IV; calcd.: 41.1%). A suggested general patꢀ
tern of the thermolysis is shown in Scheme 4. Note
that the final product combines tin and tungsten
= 130.3 2.5 kJ/mol). atoms, which are not easily compatible using convenꢀ
105–111°C
–3CO
CpMn(CO)(NO)Sn(SPh)3W(CO)5
CpMn(NO)Sn(SPh)3W(CO)3
152–270
–Ph2S2
°
C
270–400°C
–Cp, –Ph
125–145
–3CO, NO
°C
CpMnSn(SPh)3W
CpMnSn(SPh)W
MnSnSW.
Scheme 4.
For the moment, we failed to isolate complex IV atoms. The only example of the coordination of
deprived of two CO groups. As implied by this fragment to three S atoms linked by methylene
structure II [3], the relative positions of the lone bridges with the Sn atom is cited in [8]; in this
electron pairs of the S atoms hinders coordination case, the bridges make the ligand flexible and fit
of the fragment W(CO)3 to all three chalcogen for chelation (Scheme 5):
CH3
CH3
:
S
S
CO
CO
CO
CH2
CH3
CH3 Sn CH2
CH2
CH3
W
:
S
+ W(CO) (CH CN)
3
CH3 Sn CH2
S
3
3
CH2
CH2
S
:
S
CH3
CH3
Scheme 5.
A reaction of benzeneselenolate complex III with ray diffraction data (Fig. 3), structure V is symmetrical
W(CO)5THF unexpectedly gives dimeric ditungsten
complex (Scheme 6), which was isolated as brown
prismatic crystals. Structure was characterized by
and contains two perpendicular planes (Se2–W1–Se2–
W1 and Se3–W1–Se3–W1).
V
V
Although the bonds between the W atoms and
the SePh bridges (on average, 2.642(2) Å) are longer
elemental analysis, IR spectroscopy, and Xꢀray difꢀ
fraction. The IR spectrum shows bands at 1985 and
1935 cm–1 (CO stretching vibrations). According to Xꢀ than the terminal W–SePh bond (2.571(2) Å), all
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
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2011

SYNTHESIS AND MOLECULAR STRUCTURES
885
O(1)
C(1)
Se(1)
W(1)
Se(3)
Se(2A)
C(2)
O(2)
O(2A)
C(2A)
Se(3A)
Se(2)
W(1A)
Se(1A)
C(1A)
O(1A)
Fig. 3. Molecular structure of complex
V. Selected bond lengths: W–W, 2.8153(16) Å; W(1)–Se(1), 2.571(2) Å; W(1)–Se(3),
2.615(2) Å; W(1)–Se(2), 2.636(2) Å; W(1)–Se(2), 2.647(2) Å; W(1)–Se(3), 2.673(2) Å.
the bonds are substantially shorter than the sum of the ened bond between sulfur and W(CO)5 in structure IV
covalent radii (2.82 Å). It is no wonder that the W–W Likewise, strengthening of the Se–W bonds in intermeꢀ
bond (2.8153(16) Å) is also shorter than the double covaꢀ diate (Scheme 6) will weaken the Sn–Se bonds and
lent radius of tungsten (3.24 Å). As for the cause of the may result in their cleavage followed by the formation of
.
А
cleavage of the Sn–Se bonds, the weakening of the tin– dimer
chalcogen bond was distinct in the formation of a shortꢀ Watom):
V
(via elimination of one CO group from either
Ph
Se
Ph
Se
Ph
Ph
Se
Se
CO
CO
Ph
Sn Se
CO
CO
W(CO) THF
5
W
W
Mn
W
THF
Mn
CO
CO
Se
Sn(SePh)3
CO
CO
NO
CO
Se
NO
Se
Ph
Ph
Ph
Se
Ph
(
(III)
(A)
V)
Scheme 6.
In reactions of complexes II and III with a Pt0 mediate
B (Scheme 7) (as in the preceding case, the
complex, Pt(0) is oxidized into Pt(II) to give the destiny of the manganese–tin residue was not studꢀ
known complexes VI and VII, probably through interꢀ ied):
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
No. 12
2011

886
PASYNSKII et al.
Ph
Ph
Ph
Se
Ph
PPh3
PPh3
PPh
PPh3
PPh3
Ph
Ph
3
Se
Se
Pt
Pt
+
Pt
Se
Sn
Mn
THF
Mn
PPh
CO
Sn(SePh)3
3
Se
CO
NO
Ph
NO
(III
)
(
B
)
(VI and VII)
Scheme 7.
2. Pasynskii, A.A., Blokhin, A.I., Shapovalov, S.S., and
Torubaev, Yu.V., Russ. J. Inorg. Chem., vol. 52, no. 6,
p. 871.
Complexes VI and VII, which are resistant to moisꢀ
ture and atmospheric oxygen, were characterized by
elemental analysis and IR spectroscopy. Their IR
spectra show bands due to phenyl groups.
Complex VII was additionally examined by Xꢀray difꢀ
fraction; the parameters obtained are identical with
those cited in [9].
3. Blokhin, A.I., Pasynskii, A.A., Torubaev, Yu.V., and
Sheer, M., Russ. J. Coord. Chem., vol. 36, no. 4, p. 284.
4. Cordero, B., Gómez, V., PlateroꢀPrats, A.E., et al.,
Dalton Trans., 2008, no. 21, p. 2832.
5. Blake, D.M. and Roundhill, D.M., Inorg. Synth., 1978,
ACKNOWLEDGMENTS
vol. 18, p. 122.
This work was supported by the Russian Foundaꢀ
tion for Basic Research (project no. 09ꢀ03ꢀ00961), the
Division of Chemistry and Materials Sciences of the
Russian Academy of Sciences (grant OKh 1.3), and
the Presidium of the Russian Academy of Sciences
(grant 7P21).
6. Sheldrick, G.M., SHELXTLꢀ97. Version 5.50, Madiꢀ
son (WI, USA): Bruker AXS Inc., 1997.
7. Ginzburg, A.G., Bokii, N.G., Yanovsky, A.I., et al.,
J. Organomet. Chem., 1977, vol. 136, p. 45.
8. Morales, D., Prez, J., Riera, L., and Miguel, V.R.ꢀD.,
Organometallics, 2001, vol. 20, no. 22, p. 4517.
REFERENCES
9. Hannu, M.S., Oilunkaniemi, R., Laitinen, R.S., and
Ahlgen, M., Inorg. Chem. Commun., 2000, vol. 3,
p. 397.
1. Holt, M.S., Wilson, W.L., and Nelson, J.H., Chem.
Rev., 1989, vol. 89, p. 11.
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2011