Reaction of platinum complexes with (+)-α-pinene and (+)-limonene. Synthesis, molecular structure, and catalytic activity of dichloro(η 4-[p-mentha-1,8{9}-diene])platinum(II)

Article abstract of DOI:10.1134/S1070363206080226

The transformations of platinum(II) and platinum(IV) complexes with inner-and outer-sphere ligands by the action of (+)-α-pinene and (+)-limonene were studied. Reduction of the metal complex is the main process whose rate increases in the following outer-sphere ligand series: (Me ₂SO)₂H⁺ < Et₃NH⁺ < K^- < H⁺. The reaction of K₂PtCl₄ with α-pinene gave cis-terpine monohydrate and dichloro-η⁴- [p-mentha-1,8(9)-diene]platinum(II), and their structure was proved by X-ray analysis. The complex belongs to monoclinic crystal system, the Pt-Cl and Pt-C bonds therein have different lengths, the ClPtCl angle is 85.88°, and the C=C bond plane is orthogonal to the square coordination core. Dichloro-η⁴-[p-mentha-1,8(9)-diene]-platinum(II) was tested as catalyst in the hydrosilylation of acetophenone with diphenylsilane. Nauka/Interperiodica 2006.

Full text of DOI:10.1134/S1070363206080226

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 8, pp. 1288 1294.
Pleiades Publishing, Inc., 2006.
Original Russian Text
pp. 1343 1349.
D.A. de Vekki, V.M. Uvarov, V.K. Bel’skii, N.K. Skvortsov, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 8,
Reaction of Platinum Complexes with (+)- -Pinene
and (+)-Limonene. Synthesis, Molecular Structure,
and Catalytic Activity
4
of Dichloro( -[p-mentha-1,8{9}-diene])platinum(II)
D. A. de Vekkia, V. M. Uvarova, V. K. Bel’skiib, and N. K. Skvortsova
a
St. Petersburg State Institute of Technology,
Moskovskii pr. 26, St. Petersburg, 190013 Russia
b Karpov Research Physicochemical Institute, State Scientific Center of the Russian Federation, Moscow, Russia
Received January 20, 2006
Abstract The transformations of platinum(II) and platinum(IV) complexes with inner- and outer-sphere
ligands by the action of (+)- -pinene and (+)-limonene were studied. Reduction of the metal complex is the
main process whose rate increases in the following outer-sphere ligand series: (Me2SO)2H+ < Et3NH+
<
K+ < H+. The reaction of K2PtCl4 with -pinene gave cis-terpine monohydrate and dichloro- 4-[p-mentha-
1,8(9)-diene]platinum(II), and their structure was proved by X-ray analysis. The complex belongs to mono-
clinic crystal system, the Pt Cl and Pt C bonds therein have different lengths, the ClPtCl angle is 85.88 , and
the C=C bond plane is orthogonal to the square coordination core. Dichloro- 4-[p-mentha-1,8(9)-diene]-
platinum(II) was tested as catalyst in the hydrosilylation of acetophenone with diphenylsilane.
DOI: 10.1134/S1070363206080226
Monoterpenes are accessible raw materials for the
synthesis of metal complexes as promising catalysts
in organic and organometallic chemistry. The main
difficulty in the synthesis of such coordination com-
pounds originates from the low stability of mono-
terpenes in the presence of metal complexes: they
readily undergo isomerizations, polymerization [1 4],
rearrangements, oxidation [5 8], etc. Nevertheless,
we thought it to be interesting to study transforma-
tions of platinum coordination compounds in the
presence of (+)- -pinene and (+)-limonene.
nium ligands (Me2SO)2H+ considerably hinders reduc-
tion of the metal complex; even after 6 months
(CH2Cl2, platinum pinene ratio 1:50), no brown color
was observed. According to the 1H NMR data
[(CD3)2CO], after 6 days the reaction solution con-
tained traces of (Me2SO)2H+ ( 2.63 ppm, t, JPt H
=
28 Hz), geometric isomers of [Pt(Me2SO)2Cl2] ( ,
ppm: 3.58 t, JPt H = 23 Hz; 3.31 t, JPt H = 21 Hz;
cis trans ratio 7:3), trans-[Pt(Me2S)2Cl4] ( 2.59
ppm, t, JPt H = 30 Hz), uncoordinated dimethyl sulf-
oxide ( 2.52 ppm, s), and trichloro(dimethyl sulf-
oxide)platinate(II) ion [Pt(Me2SO)Cl3] ( 3.53 ppm,
Treatment of a solution of chloroplatinic acid in
propan-2-ol with excess -pinene at 20 C in 3 h led
to change of the color from orange to red and then to
black brown, indicating fast reduction of Pt(IV)
through Pt(II) to Pt(0). The 1H NMR spectrum
(CDCl3) of the reaction solution did not change;
however, after 4 days, new signals appeared as 1.07,
1.11, 1.43, 1.47, 1.63, and 1.79 ppm, i.e., transforma-
tion of the pinene skeleton occurred just in the
presence of platinum(0).
t, JPt H
=
26 Hz). The transformation of
[(Me2SO)2H]2[PtCl6] into cis-[Pt(Me2SO)2Cl2] was
reported previously [9], but the reaction occurred in
excess dimethyl sulfoxide. It is also known that trans-
[Pt(Me2S)2Cl4] is formed in the solid-phase ther-
molysis of [(Me2SO)2H]2[PtCl6]through [(Me2SO)2H]
[Pt(Me2SO)Cl5] [9]; however, the latter was not
detected in our case. Taking into account the presence
of species detected by NMR spectroscopy, cis-
[Pt(Me2SO)2Cl2] is likely to be formed according to
the following scheme:
The presence of two outer-sphere dimethylsulfoxo-
trans-[Pt(Me2SO)2Cl2] Me SO
-pinene
2
[(Me2SO)2H][Pt(Me2SO)Cl3]
[(Me2SO)2H]2[PtCl6]
cis-[Pt(Me2SO)2Cl2].
CH2Cl2
CH2Cl2
CH2Cl2
1288

REACTION OF PLATINUM COMPLEXES WITH (+)- -PINENE
1289
In the first step, dimethylsulfoxonium hexachloro-
platinate(IV) is reduced to dimethylsulfoxonium tri-
chloro(dimethyl sulfoxide)platinate(II) by the action
of -pinene, and the reduction product is gradually
transformed into readily isomerizable trans-dichloro-
bis(dimethyl sulfoxide)platinum(II). The final step is
isomerization of trans-[Pt(Me2SO)2Cl2] into the cis
complex; this process is well known [10] to readily
occur in the presence of a small amount of free di-
methyl sulfoxide (which is liberated during the
reaction).
Pt(II) to metallic platinum (the complete reduction
requires 1 month); when the above ratio is decreased,
no products are formed even after prolonged keeping
1
of the reaction mixture (8 months). The H NMR
spectrum of the reaction mixture after keeping for
5 months at 20 C coincided with that of the mixture
heated for 5 h at 60 C: new signals at 0.89, 1.01,
1.34, and 1.36 ppm appeared; these signals are likely
to belong to -terpinene and - and -fenchenes.
When the reaction was carried out under argon,
yellow crystals separated from the solution in
2 months; the product is insoluble in water and un-
stable: it quickly decomposes on exposure to air or
on further keeping in the solution); presumably, the
product is a short-lived platinum complex A with
bridging chlorine atoms and coordinated -pinene
molecules.
The reaction of bis(triethylammonium) hexachloro-
platinate(IV) with -pinene at 20 C in 2 months leads
1
to appearance in the H NMR spectrum (CDCl3) of
new signals belonging to triethylammonium chloride
[ , ppm: 1.37 t (CH3, J = 7.3 Hz), 3.08 q (CH2, J =
6.1, 7.4 Hz)] and bis(triethylammonium) tetrachloro-
platinate(II) (Et3NH)2[PtCl4] [ , ppm: 1.45 t (CH3,
J = 7.3 Hz), 3.29 q (CH2, J = 7.0 Hz)]. In the reaction
of -pinene with bis(triethylammonium) tetrachloro-
platinate(II) (3 months), the same products as in the
reaction with the Pt(IV) complex were detected in the
reaction mixture. The presence of free triethylam-
monium chloride indicates gradual decomposition of
both bis(triethylammonium) tetrachloroplatinate(II)
and bis(triethylammonium) hexachloroplatinate(IV).
K2PtCl4
Cl
Cl
Cl
Pt
Pt
Cl
A
The reaction of K2PtCl4 with -pinene in a hydro-
chloric acid solution in 6 months at 20 C leads to
platinum(II) complex with 4-coordinated limonene
[p-mentha-1,8(9)-diene]; the structure of that complex
was proved by X-ray analysis (Fig. 1). We presumed
that the isomerization of -pinene into dl-limonene is
directly related to its coordination, for the main
process in the presence of hydrochloric acid is thermal
isomerization into alloocimene [1] which was not
detected in the reaction mixture.
Apart from dichloro- 4-[p-mentha-1,8(9)-diene]-
platinum(II), 10% of terpine hydrate crystallized from
the reaction solution; its structure as cis-terpine
monohydrate was also proved by X-ray analysis
(Fig. 2; its structural parameters coincided with those
reported in [11]). In order to rule out the possibility
-pinene
(Et3NH)2[PtCl4]
(Et3NH)2[PtCl6]
-pinene
Pt + 2Et3N HCl.
The reaction of -pinene with K2PtCl4 in aqueous
solution is sensitive to the reagent substrate ratio. The
optimal ratio -pinene K2PtCl4 is 10:1; raising the
fraction of -pinene leads to gradual reduction of
C4
C3
C6
C5
C7
C9
C2
O3
C1
C8
C9
O2
C10
C5
C6
C8
O1
C7
Pt1
C4
C10
Cl1
Cl2
C1
C3
C2
4
Fig. 1. Structure of the molecule of dichloro[ -p-
mentha-1,8(9)-diene]platinum(II) according to the
X-ray diffraction data.
Fig. 2. Structure of the molecule of cis-terpine hydrate
according to the X-ray diffraction data.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 8 2006

1290
DE VEKKI et al.
for formation of terpine by the action of hydrochloric
acid, we performed special experiments. When
-pinene was treated with dilute hydrochloric acid,
no terpine signals were detected in the H NMR spec-
rum of the reaction mixture after 3 months at 20 C,
while terpine hydrate was formed on keeping a solu-
tion of -pinene and K2PtCl4 in aqueous HCl. Pre-
sumably, potassium tetrachloroplatinite promotes the
transformation of -pinene into dl-limonene and cis-
terpine hydrate according to the following scheme.
1
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Pt
A
Pt
^
Pt
K+
K2PtCl4
KCl
K+
KCl
B
C
D
K[PtCl3]
H2O
OH
OH
2H2O
H2O
H+
HO
H2O
E
F
G
In the first step potassium trichloro( 2-pinene)-
platinate(II) (B) and already noted bis[chloro( -chlo-
ro)( 2-pinene)platinum] (A) are formed. However,
taking into account stronger trans-effect of the alkene
as compared to chlorine [12, 13], dimer A should give
rise to trans-complex instead of dichloro-[ 4-p-
mentha-1,8(9)-diene]platinum(II) (D) (cis). Therefore,
the formation of complex B seems to be more prob-
able. Opening of the smaller ring in 2-coordinated
-pinene leads to more energetically favorable potas-
sium trichloro[ 2-p-mentha-1,8(9)-diene]platinate(II).
The latter is converted into either complex D or
limonene (E); the presence of limonene in the reaction
mixture is confirmed by the 13C NMR spectrum
(CDCl3), C, ppm: 20.57, 23.24, 27.72, 30.37, 30.59,
40.89, 108.17, 120.47, 133.47, 149.98.
(5 months at 20 C) gave no products D and G, and
the NMR spectra of the reaction solution coincided
almost completely with those of the reaction mixture
obtained from -pinene and K2PtCl4 under analogous
conditions. Presumably, limonene coordinates to pla-
tinum at the more reactive exocyclic double bond
(complex H) [14 16], while the endocyclic double
bond is not involved in coordination for conforma-
tional reasons (according to the X-ray diffraction data,
4-coordination of limonene strongly distorts its boat
conformation). Insofar as the NMR spectra of both re-
action solutions (obtained from limonene and -pi-
nene) are almost identical, we presume that the iso-
merization of -pinene into dl-limonene is the main
process occurring in the presence of K2PtCl4.
Cl
Cl
Cl
It is known [14] that terpine hydrate (G) is formed
by acid hydrolysis of pinene or limonene, which
involves intermediate formation of -terpineol (F).
On the other hand, hydration of the uncoordinated
double bond in the limonene molecule can occur di-
rectly in complex C with subsequent elimination of
alcohol F. This reaction pathway follows from the
results of studies on catalytic oxidation of limonene
with molecular oxygen in the presence of palladium
complexes: -terpineol was detected among the oxida-
tion products [15, 16].
Pt
K+
H
Thus, the ability of outer-sphere complexes to react
with -pinene depends on the nature of the outer-
sphere cation. The rate of decomposition of metal
The reaction of (+)-limonene with K2PtCl4
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 8 2006

REACTION OF PLATINUM COMPLEXES WITH (+)- -PINENE
1291
complexes decreases in the following series of cations:
(Me2SO)2H+ > Et3NH+ > K+ > H+.
Crystals of dichloro-[ 4-p-mentha-1,8(9)-diene]-
platinum(II) belong to the monoclinic system; the
ClPtCl angle is 85.88 , which is typical of other pla-
tinum(II) complexes with chelating ligands [17 21].
For example, the ClPtCl angle in dichloro[ 4-5-
methylidenecycloheptene]platinum(II) is 86.6 , and
in dichloro[ 4-cycloocta-1,5-diene]platinum(II)
[Pt(COD)Cl2], 89.78 . The Pt Cl bond lengths in
Apart from platinum complexes with outer-sphere
ligands, it was also interesting to examine the be-
havior of platinum(II) complexes with inner-sphere
ligands in the presence of -pinene and limonene, i.e.,
under reductive conditions. We found that cis-
[Pt(Me2SO)2Cl2] failed to react with -pinene in
methylene chloride at 20 C (3 months) and that heat-
ing of the reaction mixture (60 C, 3 h) induced fast
decomposition of the complex with liberation of
metallic platinum. Unlike -pinene, limonene pro-
moted decomposition of cis-[Pt(Me2SO)2Cl2] in 26 h
complex
[Pt(COD)Cl2] (2.310, 2.317
[17, 18], respectively; Table 1; cf. standard Pt Cl
bond length 2.303 [19]). The distances from
D
are similar to those found in
and 2.309, 2.315
platinum to the olefinic fragments are also different:
the Pt C distances to the endocyclic double bond are
2.156 and 2.269 , and to the exocyclic, 2.155 and
2.232 ; therefore, these bonds should differ in their
strength. As follows from the Pt C bond lengths,
coordination to metal does not change the order of the
double bonds to an appreciable extent (the C=C bond
1
at 20 C: In the H NMR spectrum (CDCl3) we ob-
served signals belonging to limonene, initial complex,
and free dimethyl sulfoxide ( 2.62 ppm, s), as well as
new signals indicating transformation of the terpene
skeleton ( , ppm: 1.24 s, 1.36 s, 2.19 m, and 2.33 s)
and a signal at 3.48 ppm, t (JPt H = 21 Hz); pre-
sumably, the latter corresponds to trans-[Pt(Me2SO)
lengths in complex D are 1.355 and 1.366
for the
2-limonene)Cl2].
endocyclic and exocyclic double bonds, respectively).
Both C=C bonds are almost orthogonal to the co-
ordination square plane, though the exocyclic double
bond should be expected to lie in that plane, as was
reported in [19]. The torsion angles between the
square plane and double C=C bond planes are similar
(93.61 ), the Cl1Pt1C1C2 angle is 101.35 , and the
Cl2Pt1C9C7 angle is 110.28 ; the latter values some-
what exceed those found in [Pt(COD)Cl2] [20, 21].
The two double bonds are turned apart with respect to
each other through an angle of 27.31 . As a result of
coordination, the cyclohexene skeleton of the organic
ligand adopts a distorted boat conformation, the single
C C bond lengths range from 1.510 to 1.526 , and
the bond angles range from 107.70 to 116.02 .
(
The complex cis-[Pt(MeCN)2Cl2] ( 2.66 ppm, t,
JPt H = 14 Hz) in methylene chloride turned out to be
the most stable toward reduction with -pinene. The
1H NMR spectrum (CDCl3) of the reaction mixture
(60 C, 27 h) contained signals from cis-
[Pt(MeCN)2Cl2] and its trans isomer ( 2.75 ppm, t,
JPt H = 14 Hz) at a ratio of 76:34 and a number of
signals at (ppm) 0.82 s, 0.86 s, 0.95 s, 0.99 s, 1.32
s, 1.48 s, 1.71 s, and 2.03 s due to transformation
products of -pinene.
1
The H NMR spectrum (CDCl3) of the organic
component changed even more strongly when
[Pt(MeCOD)Cl2] was used as substrate (in methylene
chloride); presumably, the reason is high lability of
1-methylcycloocta-1,5-diene (MeCOD) as ligand.
After 17 h at 60 C, the spectrum contained numerous
signals, the most intense of which were located at
0.82, 0.96, 1.28, 1.45, 1.63, 1.97, and 2.15 ppm. In
the 13C NMR spectrum (CDCl3) of the same mixture
we observed signals belonging to products of both
isomerization and rearrangement of -pinene and its
The catalytic activity of complex D was studied in
the reaction of acetophenone with diphenylsilane by
comparing with the catalytic activity of structurally
related dichloro( 4-1-methylcycloocta-1,5-diene)pla-
tinum(II) [Pt(MeCOD)Cl2]. Taking into account that
both these complexes are achiral (but asymmetric
induction was desirable), the reactions were performed
according to the standard procedure (see Experimen-
tal). Excess (+)-limonene (4 mol %) was added, and
AgBF4 was used as Lewis acid to enhance the solu-
bility and catalytic activity of the complexes.
oxidation. For example, signals at
203.82, 155.19,
C
120.72, and 57.1 ppm were assigned to 4,6,6-tri-
methylbicyclo[3.1.1]hept-3-en-2-one (I) which is
formed in the catalytic oxidation of -pinene [4, 8].
Thus [Pt(MeCOD)Cl2] cannot be used for the prepara-
tive synthesis of new monoterpene complexes, but it
can be regarded as a potential catalyst for oxidation of
monoterpenes.
Dichloro[ 4-p-mentha-1,8(9)-diene]platinum(II)
turned out to be less active but more selective catalyst
than [Pt(MeCOD)Cl2]. According to the 1H NMR data,
the yield of the corresponding silyl ether ( 1.38 ppm,
d, CH3, J = 6.0 Hz; CDCl3) at 5 C was 98% in
10 days in the presence of complex D and 100% in
5 days in the presence of [Pt(MeCOD)Cl2], and the
O
I
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 8 2006

1292
DE VEKKI et al.
Table 1. Bond angles (d) and bond angles ( ) in the mol-
ecule of dichloro[ 4-p-mentha-1,8(9)-diene]platinum(II)
Table 2. Coordinates of non-hydrogen atoms ( 104) in
the molecule of dichloro[ 4-p-mentha-1,8(9)-diene]pla-
tinum(II)
Bond
d,
Bond
d,
Atom
x
y
z
Pt C1
Pt C9
Pt C7
Pt C2
Pt Cl1
Pt Cl2
C1 C2
C1 C6
2.156(7)
2.155(9)
2.232(8)
2.269(8)
2.310(2)
2.317(2)
1.355(11)
1.525(11)
C2 C3
C2 C10
C3 C4
C4 C5
C5 C6
C5 C7
C7 C9
C7 C8
1.510(12)
1.535(12)
1.526(13)
1.511(12)
1.516(11)
1.525(11)
1.366(12)
1.513(12)
Pt
5522(1)
2996(3)
4742(4)
2527(1)
5464(2)
3878(2)
6544(5)
6808(5)
7075(5)
6799(5)
6107(5)
6435(5)
5220(5)
4447(7)
5102(6)
7187(6)
5340(1)
982(3)
Cl1
Cl2
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
2711(3)
1655(9)
2860(8)
4091(9)
4042(10)
2953(9)
1557(8)
3244(9)
2497(10)
4319(8)
2910(14)
6409(12)
5807(10)
7084(12)
9015(13)
9230(11)
8396(12)
8411(11)
9131(12)
7395(13)
3935(15)
Angle
, deg
Angle
, deg
C9PtC1
C9PtC7
C1PtC7
C9PtC2
C1PtC2
C7PtC2
C9PtCl1
C1PtCl1
C7PtCl1
C2PtCl1
C9PtCl2
C1PtCl2
C7PtCl2
C2PtCl2
Cl1PtCl2
C2C1C6
C2C1Pt
C6C1Pt
C1C2C3
104.6(3)
36.2(3)
81.8(3)
90.4(3)
35.6(3)
87.7(3)
165.2(3)
87.0(2)
157.9(2)
94.1(2)
85.9(2)
160.2(2)
98.4(2)
163.6(2)
85.88(9)
120.4(8)
76.8(4)
106.2(5)
120.9(8)
C1C2C10
C3C2C10
C1C2Pt
C3C2Pt
C10C2Pt
C2C3C4
C5C4C3
C4C5C6
C4C5C7
C6C5C7
C5C6C1
C9C7C8
C9C7C5
C8C7C5
C9C7Pt
C8C7Pt
C5C7Pt
C7C9Pt
122.1(8)
113.1(8)
67.6(4)
114.9(5)
107.5(6)
116.0(7)
112.7(7)
109.0(7)
114.6(7)
108.5(6)
107.7(7)
121.3(8)
121.9(7)
115.4(8)
68.8(5)
(13C) from solutions in CDCl3, (CD3)2SO, and
(CD3)2CO; no additional reference was added, and the
chemical shifts were measured relative to the corre-
sponding solvent signals. The IR spectra were obtained
in KBr on a Shimadzu FTIR-8400S spectrometer in
1
the range from 4000 to 500 cm . Hydrosilylation of
acetophenone with diphenylsilane was performed ac-
cording to the procedure reported in [23]. Asymmetric
induction was determined on a Perkin Elmer 241MC
polarimeter in 10-cm temperature-controlled quartz
cells.
107.7(5)
105.9(5)
75.0(5)
X-ray analysis was performed on an Enraf Nonius
CAD-4 automatic four-circle diffractometer (MoK
radiation, -filter, /2 scanning). Single crystals
for crystallographic studies were obtained from the
reaction solution by slow evaporation. Dichloro[ 4-p-
mentha-1,8(9)-diene]platinum(II):
0.38 0.14 0.14 mm, yellow prisms; monoclinic
crystal
size
selectivity was 67 and 59%, respectively. In both
cases, the subsequent hydrolysis of 1-diphenylsiloxy-
1-phenylethane gave racemic 1-phenylethanol, i.e., no
asymmetric induction was observed. Presumably, the
reason is that coordination of the silicon hydride
crystal system; unit cell parameters: a = 7.566(2), b =
15.245(3), c = 9.670(2) ; V = 1109.5(4) 3; Z = 2;
3
= 2.408 g cm ; 1340 reflections with I > 2 (I);
calc
correction for absorption of X-rays by the sample
=
(
2-coordination of silicon hydride is the key stage in
1
13.080 mm ; R = 0.0271. The structure was solved
by the heavy-atom procedure in anisotropic approxima-
tion. cis-Terpine hydrate: crystal size 0.25 0.12
0.08 mm, colorless prisms; orthorhombic crystal
system; unit cell parameters: a = 18.435(4), b =
the formation of true hydrosilylation catalyst [22])
predominates over coordination of (+)-limonene. As a
result, 4-coordinated achiral ligand is not replaced by
the optically active analog, and the true catalyst is
achiral dichloroplatinum(II) complex with 2-co-
ordinated diphenylsilane and dl-limonene.
22.817(5), c = 10.940(2) ; V = 4601.7(16) 3; Z =
3
16;
= 1.099 g cm ; 1696 reflections with I >
2 (I);calccorrection for absorption of X-rays by the
EXPERIMENTAL
1
sample
= 0.079 mm ; R = 0.0267.
1
The H and 13C NMR spectra were recorded on a
Methylene chloride (Merck), diphenylsilane (Acros),
AgBF4 (Aldrich), and chemically pure grade aceto-
Bruker AC-200 instrument at 200 (1H) and 50 MHz
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 8 2006

REACTION OF PLATINUM COMPLEXES WITH (+)- -PINENE
1293
phenone, (+)- -pinene, (+)-limonene, K2PtCl4, and
RhCl3 4H2O were used.
4. da Silva Rocha, K.A., Kozhevnikov, I.V., and Gusev-
skaya, E.V., Appl. Catal., A, 2005, vol. 294, no. 1,
p. 106.
The
complexes
cis-[Pt(Me2SO)2Cl2],
cis-
[Pt(MeCN)2Cl2], [Rh(CO)2Cl]2 [24], (Et3NH)2[PtCl4],
(Et3NH)2[PtCl6] [25], [(Me2SO)2H]2[PtCl6] [26], and
[Pt(MeCOD)Cl2] [27] were synthesized by known
methods.
5. da Silva, M.J. and Gusevskaya, E.V., J. Mol. Catal.
A: Chem., 2001, vol. 176, nos. 1 2, p. 23.
6. Lajunen, M.K., J. Mol. Catal. A: Chem., 2001,
vol. 169, nos. 1 2, p. 33.
Dichloro[ 4-p-mentha-1,8(9)-diene]platinum(II).
Potassium tetrachloroplatinate(II), 35.9 mg, and (+)- -
pinene, 0.1 ml, were dissolved in 50 ml of 0.001 N
hydrochloric acid at room temperature. After
6 months (the solution was allowed to slowly evapo-
rate), 12.7 mg of the brown complex was filtered off.
Yield 36.5%. The X-ray diffraction data (bond lengths
and angles and coordinates of non-hydrogen atoms)
7. Gonsalves, J.A., Howarth, O.W., and Gusev-
skaya, E.V., J. Mol. Catal. A: Chem., 2002, vol. 185,
nos. 1 2, p. 97.
8. Robles-Dutenhefner, P.A., da Silva, M.J., Sales, L.S.,
Sousa, E.M.B., and Gusevskaya, E.V., J. Mol. Catal.
A: Chem., 2004, vol. 217, nos. 1 2, p. 139.
9. Spevak, V.N., Cand. Sci. (Chem.) Dissertation,
1
are given in Tables 1 and 2. IR spectrum, cm : 2962
Leningrad, 1971.
(
(
C H); 2278, 2257, 2249, 2123; 1643 ( C=C); 1518
C H, ring); 1450 ( C H, ring, CH3); 1157, 1132,
10. Price, J.H., Birk, J.P., and Wayland, B.B., Inorg.
Chem., 1978, vol. 17, no. 8, p. 2245.
1020, 1008 ( C H); 841, 823 (
774 ( C C, ring); 636.
and C H); 789,
C C
11. Suga, T., Hirata, T., and Aoki, T., Bull. Chem. Soc.
Jpn., 1982, vol. 55, no. 3, p. 914.
cis-Terpine hydrate was isolated from the same
reaction solution. Yield 54.0%. The bond lengths and
bond angles determined by X-ray analysis coincided
with those reported in [11]. 1H NMR spectrum
[(CD3)2SO], , ppm: 1.00 s (6H, CH3), 1.05 s (3H,
CH3), 1.21 m (4H, CH2), 1.50 t (4H, CH2, J = 14 Hz).
12. Kukushkin, Yu.N., Reaktsionnaya sposobnost’ ko-
ordinatsionnykh soedinenii (Reactivity of Coordina-
tion Compounds), Leningrad: Khimiya, 1987
13. Metody elementoorganicheskoi khimii. Tipy metal-
loorganicheskikh soedinenii perekhodnykh metallov
(Methods of Organometallic Chemistry. Types of
Organometallic Compounds Formed by Transition
Metals), Nesmeyanov, A.N. and Kocheshkov, K.A.,
Eds., Moscow: Nauka, 1975.
1
IR spectrum, cm : 3480, 3250 ( O H); 2966, 2830
(
C H); 1639 ( O H); 1385, 1312, 1255 (
and
C O
C H); 1242, 1222, 1178, 1135 (
and C H); 1118,
1016, 990, 954, 933, 904, 839 ( C O and C H); 772,
O H
724, 655, 604, 462, 457, 451, 441, 436, 426, 400
(
and C H).
C C
14. Plemenkov, V.V., Vvedenie v khimiyu prirodnykh
soedinenii (Introduction to the Chemistry of Natural
Compounds), Kazan: Mariiskii, 2001.
ACKNOWLEDGMENTS
This study was financially supported by the Rus-
15. Gusevskaya, E. and Gonsalves, J.A., J. Mol. Catal. A:
Chem., 1997, vol. 121, nos. 2 3, p. 131.
sian Foundation for Basic Research (project nos. 04-
03-32632a, 06-03-32137a), by the President of
the Russian Federation (project no. MK-3204. 2005.3),
and by the Government of St. Petersburg (project
no. PD05-1.3-20).
16. Gusevskaya, E.V., Quim. Nova, 2003, vol. 26, no. 2,
p. 242.
17. Syed, A., Stevens, E.D., and Cruz, S.G., Inorg. Chem.,
1984, vol. 23, no. 22, p. 3673.
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