Synthesis and structure of the platinum complexes [Bu4N] +[PtBr5(DMSO)]-, [Ph4P] +[PtBr5(DMSO)]-, and [Ph3(n-Am)P] +[PtBr5(DMSO)]-

Article abstract of DOI:10.1134/S1070328411100113

The complexes [Bu₄N] ₂ ⁺ [PtBr ₆]^2- (I), [Ph₄P] ₂ ⁺ [PtBr₆]^2- (II), and [Ph₃(n-Am)P] ₂ ⁺ (III) are synthesized by the reactions of tetrabutylammonium bromide, tetraphenylphosphonium bromide, and triphenyl(n-amyl)- tetraphenylphosphonium bromide, respectively, with potassium hexabromoplatinate (mole ratio 2: 1). After recrystallization from dimethyl sulfoxide, complexes I, II, and III transform into [Bu₄N]⁺[PtBr ₅(DMSO)]^- (IV), [Ph₄P]⁺[PtBr ₅(DMSO)]^- (V), and [Ph₃(n-Am)P] ⁺[PtBr₅(DMSO)]^- (VI). According to the X-ray diffraction data, the cations of complexes IV-VI have a slightly distorted tetrahedral structure. The N-C and P-C bond lengths are 1.492(7)-1.533(6) and 1.782(10)-1.805(10) A, respectively. The platinum atoms in the mononuclear anions are hexacoordinated. The dimethyl sulfoxide ligands are coordinated with the Pt atom through the sulfur atom (Pt-S 2.3280(18)-2.3389(11) A). The Pt-Br bond lengths are 2.4330(6)-2.4724(6) A.

Full text of DOI:10.1134/S1070328411100113

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2011, Vol. 37, No. 11, pp. 854–860. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © V.V. Sharutin, V.S. Senchurin, O.K. Sharutina, N.V. Somov, A.V. Gushchin, 2011, published in Koordinatsionnaya Khimiya, 2011, Vol. 37, No. 11,
pp. 857–863.
Synthesis and Structure of the Platinum Complexes
[Bu4N]+[PtBr5(DMSO)]–, [Ph4P]+[PtBr5(DMSO)]–,
and [Ph3(n
ꢀAm)P]+[PtBr5(DMSO)]–
V. V. Sharutina, *, V. S. Senchurina, O. K. Sharutinaa, N. V. Somovb, and A. V. Gushchinb
a Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
b Nizhnii Novgorod State University, Nizhnii Novgorod, 603600 Russia
* eꢀmail: vvsharutin@rambler.ru
Received February 11, 2011
+
2−
+
2−
2−
Abstract—The complexes
(I),
(
II), and [Ph3(nꢀAm)P]+2
PtBr
6
(
III
are synthesized by the reactions of tetrabutylammonium bromide, tetraphenylphosphonium bromide, and triꢀ
phenyl( ꢀamyl)ꢀtetraphenylphosphonium bromide, respectively, with potassium hexabromoplatinate (mole ratio
2 : 1). After recrystallization from dimethyl sulfoxide, complexes II, and III transform into
[Bu4N]+[PtBr5(DMSO)]– IV), [Ph4P]+[PtBr5(DMSO)]– ), and [Ph3(nꢀAm)P]+[PtBr5(DMSO)]–
VI).
According to the Xꢀray diffraction data, the cations of complexes IV VI have a slightly distorted tetrahedral
structure. The N–C and P–C bond lengths are 1.492(7)–1.533(6) and 1.782(10)–1.805(10) Å, respectively.
The platinum atoms in the mononuclear anions are hexacoordinated. The dimethyl sulfoxide ligands are
)
Bu N PtBr
Ph P PtBr
[
]2 [
]
[
]2 [
]
[
]
4
6
4
6
n
I,
(
(V
(
–
coordinated with the Pt atom through the sulfur atom (Pt–S 2.3280(18)–2.3389(11) Å). The Pt
lengths are 2.4330(6)–2.4724(6) Å.
⎯Br bond
DOI: 10.1134/S1070328411100113
+
2−
In continuation of the study of the reactions of
inorganic platinum salts with onium compounds of
the 15 Group elements [1–3], we synthesized tetrabuꢀ
tylammonium, tetraphenylphosphonium, and tripheꢀ
Synthesis of
(II). Potassium
Ph P PtBr
]2 [
[
]
4
6
hexabromoplatinate (0.15 g, 0.20 mmol) was disꢀ
solved on heating in 15 ml of distilled water, and tetraꢀ
phenylphosphonium bromide (0.17 g, 0.40 mmol) in
water (15 ml) was added to the solution with stirring. A
yellowꢀorange precipitate was formed, filtered off,
washed with distilled water, and dried. The yield of
nyl(nꢀamyl)phosphonium hexabromoplatinates by
the reaction of potassium hexabromoplatinate with
ammonium and phosphonium bromides in water and
studied the structures of the products of their reactions
with dimethyl sulfoxide.
complex II was 0.25 g (93%),
Tdecomp = 255°C.
IR,
ν
, cm–1: 528, 690, 723, 753, 762, 996, 1107,
1165, 1190, 1316, 1435, 1440, 1483, 1584, 3053.
EXPERIMENTAL
+
2−
For C48H40P2Br6Pt
Synthesis of
(I). Potassium
Bu N PtBr
]2 [
[
]
4
6
anal. calcd., %:
Found, %:
C, 42.57;
C, 42.47;
H, 2.97.
H, 3.07.
hexabromoplatinate (0.15 g, 0.20 mmol) was dissolved
on heating in 15 ml of distilled water, and tetrabutylꢀ
ammonium bromide (0.13 g, 0.40 mmol) in water
(5 ml) was added to the solution with stirring. A yelꢀ
lowꢀorange precipitate was formed, filtered off,
washed with distilled water, and dried. The yield of
was 0.17 g (74%),
, cm–1: 739, 882, 1030, 1068, 1154, 1169,
1379, 1471, 2872, 2959, 3442.
Synthesis of [Ph3(nꢀAm)P]+2
sium hexabromoplatinate (0.15 g, 0.20 mmol) was disꢀ
solved on heating in 15 ml of distilled water, and triꢀ
(III). Potasꢀ
2−
PtBr
[
]
6
complex
I
Tdecomp = 240°C.
phenyl(nꢀamyl)phosphonium bromide (0.17 g,
0.40 mmol) in water (15 ml) was added to the solution
with stirring. A yellowꢀorange precipitate was formed,
filtered off, washed with distilled water, and dried. The
IR,
ν
yield of complex III was 0.23 g (86%), Tdecomp
>
ForC32H72N2Br6Pt
220°C.
IR,
, cm–1: 5077, 534, 692, 724, 749, 997, 1113,
ν
anal. calcd., %:
Found, %:
C, 33.13;
C, 33.00;
H, 6.21.
H, 6.54.
1164, 1188, 1314, 1336, 1437, 1483, 1586, 2359, 2923,
2953, 3055, 3081.
854

SYNTHESIS AND STRUCTURE OF THE PLATINUM COMPLEXES
855
determined by a direct method and refined by the fullꢀ
matrix leastꢀsquares method in the anisotropic
approximation for nonꢀhydrogen atoms (SHELXꢀ97,
WinGX) [5, 6]. Positions of hydrogen atoms were
determined geometrically by the riding model. The
main crystallographic data and results of refinement of
structures IV–VI are given in Table 1. Selected bond
lengths and bond angles are listed in Table 2.
The full tables of coordinates of atoms and bond
lengths and bond angles were deposited with the Camꢀ
bridge Crystallographic Data Centre (nos. 815004
For C46H52P2Br6Pt
anal. calcd., %:
Found, %:
C, 41.16;
C, 39.87;
H, 3.88.
H, 3.96.
Synthesis of [Bu4N]+[PtBr5(DMSO)]– (IV)
plex (0.08 g, 0.07 mmol) was dissolved with stirring
. Comꢀ
I
in dimethyl sulfoxide (5 ml). A red solution was conꢀ
centrated, and the red needleꢀlike crystals that formed
were filtered off and dried. The yield of complex IV
was 0.58 g (92%),
Tdecomp = 180°C.
(
IV), 815005 (V), and 815006 (VI); deposit@ccdc.
IR,
ν
, cm–1: 425, 737, 882, 1025, 1169, 1311, 1381,
cam.ac.uk; http://www.ccdc.cam.ac.uk).
1470, 2873, 2961, 3434.
RESULTS AND DISCUSSION
For C18H42NOSBr5Pt
anal. calcd., %:
Found, %:
The syntheses and structures of the bromineꢀconꢀ
taining platinum complexes were described for single
examples of the mononuclear [PtBr6]2–, binuclear
[Pt2Br9]– and trinuclear [Pt3Br12]2–, anions [7].
We found that the reactions of tetrabutylammoꢀ
nium, tetraphenylphosphonium, and triphenylꢀ
amylphosphonium bromides with potassium hexabroꢀ
moplatinate at a mole ratio of the reactants of 2 : 1 in
water afforded yellowꢀorange finely crystalline comꢀ
C, 23.62;
C, 23.53;
H, 4.59.
H, 4.68.
Synthesis of [Ph4P]+[PtBr5(DMSO)]– (V)
. Comꢀ
plex II (0.15 g, 0.11 mmol) was dissolved with stirring
in dimethyl sulfoxide (5 ml). A red solution was conꢀ
centrated, and the red crystals that formed were filꢀ
tered off and dried. The yield of complex
V
was 0.10 g
(91%),
IR,
Tdecomp = 204°C.
pounds I, II, and III with the Ptꢀcontaining anions.
ν
, cm–1: 528, 688, 724, 756, 761, 994, 1026,
+
2−
−
+
1108, 1160, 1167, 1312, 1437, 1482, 1585, 2920, 3006,
3034, 3053, 3077.
2 R E Br + K PtBr
[
]
[
]
4
2
6
+
2−
H2O
⎯⎯⎯→ R E PtBr
+ 2KBr,
[
]2 [
]
4
6
For C26H26OPSBr5Pt
E = N,R = Bu; E = P,R = Ph, nꢀAm.
anal. calcd., %:
Found, %:
C, 30.84;
C, 30.59;
H, 2.57.
H, 2.66.
We found that the dissolution of compounds I–III
in dimethyl sulfoxide resulted in ligand exchange in
the anion, which was accompanied by a change in the
yellow color of the solution to redꢀbrown. The reacꢀ
tion products are the complexes with mixedꢀligand
Synthesis of [Ph3(n .
ꢀAm)P]+[PtBr5(DMSO)]– (VI)
A mixture of potassium hexabromoplatinate (0.15 g,
0.2 mmol), triphenylꢀnꢀamylphosphonium bromide
anions (IV–VI).
(0.08 g, 0.2 mmol), and dimethyl sulfoxide (5 ml) was
stirred at 20°C for 5 min. A red solution was concenꢀ
trated, and the red crystals that formed were filtered
off and dried. The yield of complex VI was 0.18 g
+
2−
R E PtBr
]2 [
[
]
4
6
+
−
+
−
DMSO
⎯⎯⎯⎯→ R E PtBr DMSO + R E Br ,
(
)
]
[
]
[
[
]
4
5
4
E = N,R = Bu; E = P,R = Ph, nꢀAm.
(90%),
IR,
Tdecomp = 220°C.
ν
, cm–1: 507, 534, 692, 724, 748, 997, 1025,
The compounds of this type can be obtained
directly from tetraorganylammonium or phosphoꢀ
nium bromide and potassium hexabromoplatinate in
dimethyl sulfoxide at a mole ratio of the reactants of 1 : 1:
1113, 1437, 2853, 2871, 2918, 2953, 3055, 3080.
For C25H32OPSBr5Pt
+
2−
−
+
Ph (nꢀAm)P Br + K PtBr
6
[
]
[
]
3
2
anal. calcd., %:
Found, %:
C, 29.83;
C, 30.03;
H, 3.18.
H, 3.28.
+
−
DMSO
⎯⎯⎯⎯→ Ph (nꢀAm)P PtBr DMSO
(
)
]
[
]
[
3
5
+ 2KBr.
–VI are red and soluble in polar
The IR spectra of complexes
I
–
VI were recorded
on a 1201 FTIR spectrometer in KBr pellets.
Xꢀray diffraction analyses of crystals IV
carried out on an Xcalibur, Sapphire3, Gemini S difꢀ
fractometer (Mo radiation,
= 0.71073 Å, tube [Bu4N]+, [Ph4P]+, and [Ph3(
operation mode 50/40 kV/mA, graphite monochroꢀ IV VI have a weakly distorted tetrahedral structure.
mator). An absorption correction was applied numerꢀ The bond angles CNC and CPC (107.4(3) –112.7(3)
, and 108.1(2) –
The crystals of IV
organic solvents.
–VI were
According to the Xꢀray diffraction data, the cations
K
λ
n
ꢀAm)P]+ of complexes
α
, V,
°
°
ically by the crystal shape [4]. The structures were in IV
,
105.4(5)
°
–112.9(6)
°
in
V
°
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
No. 11
2011

856
SHARUTIN et al.
Table 1. Crystallographic data and experimental and refinement parameters for the structures of complexes IV–VI
Value
Parameter
IV
V
VI
T
, K
298(2)
298(2)
293(2)
Orthorhombic
21L121
Crystal system
Space group
Monoclinic
Triclinic
P
21/n
P
P1
7.9290(4)
13.3730(8)
14.5704(7)
79.092(4)
87.763(4)
88.607(4)
1515.66(14)
2
a
, Å
, Å
11.5329(3)
21.5469(13)
23.3728(7)
90
11.8019(2)
12.7545(2)
20.4615(4)
90
b
c,
, deg
, deg
Å
α
β
91.289(3)
90
90
γ, deg
90
3
V
Z
ρ
μ
, Å
5806.6(4)
8
3080.01(9)
4
3
calcd, g/cm
2.092
2.218
2.170
–1
, mm
11.796
3464
11.36
11.179
1896
F
(000)
Crystal size, mm
range of data collection, deg
948
0.2975
×
0.1483
×
0.1127 0.4147
×
0.1858
×
0.0855 0.3457
×
0.2309
×
0.1327
ρ
3.46–30.51
3.46–30.51
3.35–30.51
Ranges of reflection indices
–16
–30
–32
≤
≤
≤
h
k
l
≤
15
29
–11
–19
–13
≤
≤
≤
h
k
l
≤
11
19
–16
–18
–29
≤
≤
≤
h
k
l
≤
16
17
22
≤
≤
≤
≤
33
≤
20
≤
Measured reflections
46450
int = 0.0848)
14644
int = 0.0288)
27364
9382 (Rint = 0.0498)
Independent reflections
17010 (
R
9131 (
R
Reflections with
I
> 2σ(I
)
5840
487
5086
317
6518
307
Refinement variables
Goodnessꢀofꢀfit
0.67
1.114
0.504
R
R
factors on F2 > 2
σ
(
F2
)
R
1 = 0.042, wR2 = 0.0625
R
R
1 = 0.0615, wR2 = 0.1892
1 = 0.1156, wR2 = 0.2008
–1.926/3.739
R
1 = 0.0299, wR1 = 0.0503
1 = 0.0555, wR1 = 0.0574
–1.06/1.086
factors on all reflections
R
1 = 0.1825, wR2 = 0.0798
R
Residualelectrondensity(min/max),
/Å3
–0.766/1.114
e
(Δ/ρ
)max/(Δ/ρ
)
0.039/0.002
0.003/0.001
0.003/0
min
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SYNTHESIS AND STRUCTURE OF THE PLATINUM COMPLEXES
857
Table 2. Selected bond lengths (
d
) and bond angles (
ω
) in the structures of compounds IV–VI
Bond
d,
Å
Angle
ω
, deg
IV
Pt(1)–S(2)
Pt(1)–Br(8)
Pt(1)–Br(2)
Pt(1)–Br(10)
Pt(1)–Br(7)
Pt(1)–Br(3)
Pt(2)–S(1)
Pt(2)–Br(5)
Pt(2)–Br(6)
Pt(2)–Br(9)
Pt(2)–Br(4)
Pt(2)–Br(1)
2.3280(18)
2.4479(8)
2.4531(6)
2.4575(6)
2.4618(6)
2.4641(6)
2.3398(18)
2.4330(6)
2.4543(7)
2.4575(6)
2.4685(8)
2.4724(6)
Br(5)Pt(2)Br(1)
Br(6)Pt(2)Br(1)
Br(9)Pt(2)Br(1)
Br(4)Pt(2)Br(1)
O(2)S(1)C(21)
O(2)S(1)C(23)
C(21)S(1)C(23)
O(2)S(1)Pt(2)
C(21)S(1)Pt(2)
C(23)S(1)Pt(2)
O(1)S(2)C(22)
O(1)S(2)C(24)
V
89.46(2)
177.57(2)
90.45(2)
89.68(3)
111.0(4)
104.7(3)
99.8(4)
115.81(19)
112.5(3)
111.5(3)
105.3(4)
106.5(4)
Pt(1)–S(1)
Pt(1)–Br(4)
Pt(1)–Br(3)
Pt(1)–Br(1)
Pt(1)–Br(2)
Pt(1)–Br(5)
2.332(3)
S(1)Pt(1)Br(4)
S(1)Pt(1)Br(3)
Br(4)Pt(1)Br(3)
S(1)Pt(1)Br(1)
Br(4)Pt(1)Br(1)
Br(3)Pt(1)Br(1)
VI
90.52(9)
88.59(9)
89.23(6)
90.26(9)
179.16(6)
91.08(5)
2.4525(13)
2.4583(15)
2.4611(13)
2.4620(13)
2.4625(15)
Pt(1)–S(1)
Pt(1)–Br(2)
Pt(1)–Br(3)
Pt(1)–Br(5)
Pt(1)–Br(4)
Pt(1)–Br(1)
2.3389(11)
2.4568(5)
2.4597(5)
2.4613(5)
2.4641(5)
2.4657(5)
S(1)Pt(1)Br(2)
S(1)Pt(1)Br(3)
Br(2)Pt(1)Br(3)
S(1)Pt(1)Br(5)
Br(2)Pt(1)Br(5)
Br(3)Pt(1)Br(5)
95.11(3)
92.02(3)
89.357(19)
175.25(3)
88.88(2)
90.582(19)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
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858
SHARUTIN et al.
Br(4)
Br(1)
Br(9)
Br(6)
C(39)
Pt(2)
C(27)
O(2)
C(37)
C(14)
S(1)
C(25)
C(15)
C(1)
Br(5)
C(23)
C(21)
C(17)
C(13)
C(19)
C(28)
C(5)
C(10)
C(6)
N(1)
C(8)
C(30)
N(2)
C(29)
C(18)
C(11)
C(2)
C(3)
C(36)
C(26)
C(7)
C(16)
Br(10)
C(9)
C(32)
C(20)
C(4)
Br(2)
O(1)
C(31)
C(40)
C(38)
S(2)
Br(8)
C(24)
Pt(1)
Br(3)
C(22)
Br(7)
Fig. 1. Structure of complex IV
.
C(11)
C(10)
C(12)
C(9)
C(21)
C(26)
C(13)
C(8)
C(23)
C(14)
C(19)
C(22)
C(25)
C(6)
P(1)
S(1)
O(1)
C(15)
C(16)
C(18)
C(17)
C(2)
Br(1)
C(24)
C(7)
Br(5)
C(4)
Pt(1)
Br(3)
C(3)
C(20)
C(1)
Br(4)
C(5)
Br(2)
Fig. 2. Structure of complex
V.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
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SYNTHESIS AND STRUCTURE OF THE PLATINUM COMPLEXES
859
C(21)
C(22)
C(23)
C(6)
C(7)
C(4)
C(3)
C(9)
C(12)
C(19)
C(15)
C(16)
Br(2)
C(1)
C(2)
C(17)
P(1)
O(1)
C(20)
S(1)
C(5)
C(10)
C(14)
Br(4)
Pt(1)
C(8)
C(24)
C(13)
Br(3)
Br(5)
Br(1)
C(11)
C(18)
C(25)
Fig. 3. Structure of complex VI
.
IV
V
VI
Fig. 4. Ion packing in complexes IV
⎯
VI (view along the
No. 11
z
axis).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
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860
SHARUTIN et al.
111.2(2)
° in (VI) differ slightly from a theoretical value VI are equal to 177.05(4)°, 178.94(9)°, 175.25(3)°, respecꢀ
tively.
of 109.5
°
. Crystal IV contains two types of crystalloꢀ
graphically independent cations [Bu4N]+ and two
The packing of cations and anions in complexes IV–VI
is shown in Fig. 4.
types of crystallographically independent anions
[PtBr5(DMSO)]–
.
REFERENCES
The platinum atoms in the anions of complexes IV–VI
have octahedral coordination. The equatorial plane of the
octahedron contains four bromine atoms, and the axial
positions are occupied by the bromine atoms and sulfur
atoms of dimethyl sulfoxide (Figs. 1–3). The platinum
atoms lie rigidly in the equatorial plane PtBr4, although the
axial positions of the octahedron contain ligands different
in type and volume: bromine and dimethyl sulfoxide. The
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(http://www.ccdc.cam.ac.uk; AXELEW, KOYDIL,
AFECOE).
Pt–S distances in the anions of complexes IV–VI are
shorter than the sum of van der Waals radii of platinum and
sulfur (3.5 Å [8]). In IV and VI, the Pt–S bonds are shortꢀ
ened almost equally (2.332(3)–2.340(2) Å) compared to
the sum of covalent radii (2.41 Å [8]). On the contrary, the
Pt–Br bond lengths (2.4330(6)–2.4724(6) Å) approach in
value the sum of covalent radii of the platinum and broꢀ
mine atoms (2.46 Å [8]). The bond angles BraxPtBreq and
SPtBreq differ slightly from a theoretical value of 90°. The
8. Cordero, B., Gromez, V., PlateroꢀPrats, A.E., et al.,
axial angles SPtBrax in the anions of complexes IV, V, and
Dalton Trans., 2008, p. 2832.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
No. 11
2011