New rhenium(III) complexes with fluorinated β-diketones

Article abstract of DOI:10.1134/S1070328412030037

Five new rhenium(III) complexes of the general formula ReCl ₂(R_FCOCHCOR_F)(PPh₃)(OPPh ₃), where R_F = CF₃ (I), C₂F ₅ (II), C₃F₇ (III), C₄F₉ (IV), and CF₃CFOC₃F₇ (V), were synthesized. The known rhenium(V) complex ReOCl₂(OC₂H₅) (PPh₃)₂, which can readily be obtained from metallic rhenium, was used as a precursor. Two polymorphous modifications of compound I were found and studied by X-ray diffraction analysis. The thermal properties of the synthesized complexes were characterized by the DTA-TG method. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070328412030037

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2012, Vol. 38, No. 3, pp. 200–206. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © D.V. Drobot, M.A. Kurykin, A.I. Irtegov, V.N. Khrustalev, M.I. Buzin, L.V. Gumileva, 2012, published in Koordinatsionnaya Khimiya, 2012, Vol. 38,
No. 3, pp. 210–216.
Dedicated to Professor Vladimir Fedorov
on the occasion of his 75th birthday
New Rhenium(III) Complexes with Fluorinated βꢀDiketones
D. V. Drobota, M. A. Kurykinb, *, A. I. Irtegova, V. N. Khrustalevb, M. I. Buzinb, and L. V. Gumilevab
a Lomonosov State Academy of Fine Chemical Technology, pr. Vernadskogo 86, Moscow, 117571 Russia
b Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, 119991 Russia
*eꢀmail: mak@ineos.ac.ru
Received September 20, 2011
Abstract—Five new rhenium(III) complexes of the general formula ReCl2(RFCOCHCORF)(PPh3)(OPPh3),
where RF = CF3 (I), C2F5 (II), C3F7 (III), C4F9 (IV), and CF3CFOC3F7 (V), were synthesized. The known rheꢀ
nium(V) complex ReOCl2(OC2H5)(PPh3)2, which can readily be obtained from metallic rhenium, was used as a
precursor. Two polymorphous modifications of compound were found and studied by Xꢀray diffraction analysis.
I
The thermal properties of the synthesized complexes were characterized by the DTA–TG method.
DOI: 10.1134/S1070328412030037
Complexes of many transition metals with polyfluꢀ phine oxide)(triphenylphosphine) (I). A solution of
orinated βꢀdiketones are known to possess a high vapor ReОСl2(OC2H5)(PPh3)2 (1 g, 1.19 mmol) and an
pressure and can often be transformed into vapor withꢀ excess of CF3COCH2COCF3 (3 g, 14.42 mmol) in
out decomposition [1]. This makes it possible to use benzene (40 mL) was refluxed for 20 min (dark blue
them, on the one hand, in the production of metalꢀconꢀ solution). The reaction mixture was transferred to a
taining film coatings by the MOCVD methods.
beaker and diluted with petroleum ether (50 mL) at
70–100 (octane can also be used). The dark blue
plateꢀlike crystals that formed were separated by filꢀ
°
С
On the other hand, interest in the development of
various rheniumꢀcontaining functional materials
increases in recent years. The rhenium complexes with
tration, washed with hexane, and dried in vacuo
(
Р
= 9 mm Hg). The yield was 1.1 g (90%), Tm
=
fluorinated
in the CVD processes. However, data on fluorineꢀconꢀ
taining rhenium ꢀdiketonates are restricted.
Three fluorineꢀcontaining rhenium(III) comꢀ
plexes with ꢀdiketones have been described
to the present time: two heteroligand complexes
ReСl2(CF3COCHCOCН3)(PPh3)2 and
βꢀdiketones could be promising for the use
200 . Compound is soluble in acetone, benzene,
°
С
I
chloroform, and CCl4; restrictedly soluble in ethaꢀ
nol and sulfuric ether; very restrictedly soluble in
cyclohexane and hexane; and insoluble in petroꢀ
leum ether (70–100°C) and octane.
β
β
For C41H31Cl2F6O3P2Re
ReСl2(CF3COCHCOCF3)(PPh3)2 [2–5] and one
monoligand complex Re(CF3COCHCOCF3)3 [6, 7].
Thus, an urgent problem and the task of the present
work are the development of methods for the synthesis
anal. calcd, %: C, 49.01; H, 3.11; Cl, 7.06; F, 11.34; P, 6.16.
Found, %:
C, 48.89; H, 3.03; Cl, 6.82; F, 11.19; P, 6.08.
of the rhenium complexes with fluorinated βꢀdikeꢀ
tones and the study of their structural characteristics
and thermal properties.
Synthesis of rhenium dichloro(1,1,1,2,2,6,6,7,7,7ꢀ
decafluoroꢀ3,5ꢀheptanedionate)(triphenylphosphine
oxide)(triphenylphosphine) (II).
A
solution of
ReОСl2(OC2H5)(PPh3)2 (0.96 g, 1.14 mmol) and
C2F5COCH2COC2F5 (0.37 g, 1.20 mmol) in benzene
(40 mL) was refluxed for 20 min. The reaction mixture
was transferred to a beaker, diluted with octane
(50 mL), and left to stay for 5 days. The mother liquor
was decanted, and the residue was dried in air.
The dark blue plateꢀlike crystals with Tm = 194°С and
Tdecomp = 250°C were obtained. The yield of comꢀ
pound II was 1.17 g (93%). Compound II is soluble in
EXPERIMENTAL
Complex ReОСl2(OCH2CH3)(PPh3)2, being the
precursor for the synthesis of the target products, was
synthesized by a described procedure [8].
For C38H35Cl2O2P2Re
anal. calcd, %:
Found, %:
C, 54.16; H, 4.19; Cl, 8.41; P, 7.35.
C, 54.14; H, 4.21; Cl, 8.48; P, 7.38.
Synthesis of rhenium dichloro(1,1,1,5,5,5ꢀ acetone, benzene, and chloroform; restrictedly soluble
hexafluoroꢀ2,4ꢀpentanedionate)(triphenylphosꢀ in CCl4; and insoluble in alcohol, hexane, and octane.
200

NEW RHENIUM(III) COMPLEXES WITH FLUORINATED
β
ꢀDIKETONES
201
For C49H31Cl2F22O5P2Re
anal. calcd, %: C, 40.96; H, 2.17; Cl, 4.93; F, 29.09.
Found, %: C, 40.74; H, 2.11; Cl, 4.89; F, 28.51.
For C43H31Cl2F10O3P2Re
anal. calcd, %: C, 46.75; H, 2.82; Cl,6.42; F, 17.20; P, 5.61.
Found, %:
C, 46.97; H, 2.63; Cl,6.30; F, 16.90; P, 5.58.
Elemental analyses for complexes I–V were carried
Synthesis
of
rhenium
dichloro(1,1,1,
out at the Laboratory of Microanalysis of the Institute
of Organoelement Compounds (Russian Academy of
Sciences). The DTA–TG studies were carried out on
a DerivatographꢀC instrument (MOM, Hungary) at
2,2,3,3,7,7,8,8,9,9,9ꢀtetradecafluoroꢀ4,6ꢀnonanediꢀ
onate)(triphenylphosphine oxide)(triphenylphosphine)
(III). Similarly to the synthesis of compound II, the
grayꢀblue crystals of complex III with
T
m= 160°C and
a heating rate of 10°C/min in argon and in air with
Tdecomp 200°C were obtained
=
from
~15ꢀmg samples. The temperature was measured with
a platinum–platinorhodium thermocouple. The temꢀ
perature corresponding to the 5% mass loss by the
sample (Тd5%) was accepted as the temperature of mass
loss onset. No intermediate products were isolated.
ReОСl2(OC2H5)(PPh3)2 (0.7 g, 0.83 mmol) and
C3F7COCH2COC3F7 (0.41 g, 1.00 mmol). The crysꢀ
tals were dried in vacuo. The yield was 0.91 g (91%).
Compound III is soluble in acetone, benzene, sulfuric
ether, chloroform, dichloromethane, and CCl4;
restrictedly soluble in alcohol; and very restrictedly
soluble in hexane.
The Xꢀray diffraction analyses for two modificaꢀ
tions of compound I (a and b) were carried out on a
Bruker APEX II CCD automated diffractometer (
100 K, MoKα radiation, graphite monochromator,
and scan modes). An Xꢀray radiation correction for
T =
For C45H31Cl2F14O3P2Re
ϕꢀ
ω
anal. calcd, %:
Found, %:
C, 44.86;
C, 44.92;
H, 2.59;
H, 2.47;
P, 5.14.
P, 5.10.
the data obtained was applied using the SADABS proꢀ
gram. Structures Ia and Ib were determined by a direct
method and refined by the fullꢀmatrix leastꢀsquare
method in the anisotropic approximation for nonꢀ
hydrogen atoms. The positions of all hydrogen atoms
were calculated from the geometric concepts and
included into the refinement in the isotropic approxiꢀ
mation along with nonꢀhydrogen atoms. All calculaꢀ
tions were performed using the SHELXTL program
package. The crystallographic characteristics and
details of the Xꢀray diffraction experiment and strucꢀ
ture refinement are given in Table 1. Selected interꢀ
atomic distances and bond angles are listed in Table 2.
Synthesis of rhenium dichloro(1,1,1,2,2,3,
3,4,4,8,8,9,9,10,10,11,11,11ꢀoctadecafluoroꢀ5,7ꢀ
undecanedionate)(triphenylphosphine oxide)(tripheꢀ
nylphosphine) ( IV). Complex IV was synthesized simꢀ
ilarly from ReОСl2(OC2H5)(PPh3)2 (1 g, 1.19 mmol)
and C4F9COCH2COC4F9 (0.7 g, 1.38 mmol). The
best dark blue plateꢀlike crystals were formed, when
octane (~50 mL) was added to an equal volume of a
hot benzene solution. Compound IV was dried in air.
The yield was 1.36 g (88%), Tm = 171°C, and Tdecomp =
235°C. Compound IV is soluble in acetone, benzene,
sulfuric ether, chloroform, dichloromethane, and
CCl4; restrictedly soluble in alcohol; very restrictedly
soluble in hexane; and insoluble in octane.
RESULTS AND DISCUSSION
In the most part of cases, the traditional methods
for the preparation of fluorineꢀcontaining transition
metal βꢀdiketonates based on exchange reactions canꢀ
not be applied to rhenium compounds, since simple
rhenium salts necessary for these processes to occur
are poorly accessible or unknown.
For C47H31Cl2F18O3P2Re
anal. calcd, %: C, 43.26; H,2.39; Cl, 5.43; F, 26.20; P, 4.74.
Found, %:
C, 43.11; H,2.33; Cl, 5.22; F, 25.96; P, 4.77.
We used the described and easily obtained complex:
rhenium oxodichloroethoxybis(triphenylphosphine)
[8]. The procedure of the synthesis includes the dissoꢀ
lution of metallic rhenium in 30% hydrogen peroxide
with the formation of rhenium acid. The resulting colꢀ
orless solution of HReO4 was evaporated by ~10 times,
and HCl and ethanol were added. Then the solution
was heated, and boiling ethanol saturated with tripheꢀ
nylphosphine was poured to the solution. A green
crystalline substance precipitated immediately, being
the desired complex used for the synthesis of fluorineꢀ
Synthesis of rhenium dichloro{1,3ꢀbis(3ꢀoxaperfluꢀ
oroꢀ2ꢀhexyl)ꢀ1,3ꢀpropanedionate}(triphenylphosꢀ
phine oxide)(triphenylphosphine) (V). Complex
V was
synthesized similarly from ReОСl2(OC2H5)(PPh3)2
(0.5 g, 0.59 mmol) and {C3F7ОCF(CF3)CO}2CH2
(0.42 g, 0.65 mmol). Crystallization from the solution
after the addition of octane occurred very slowly, and
the most complete precipitation was attained after
18 days. Compound
0.75 g (88%), Tm = 155°C, and Tdecomp = 160°C.
Compound is a dark blueꢀviolet powder soluble in
V was dried in air. The yield was
V
containing rhenium βꢀdiketonates.
acetone, benzene, sulfuric ether, chloroform, dichloꢀ
romethane, CCl4, and alcohol; very restrictedly soluꢀ
ble in hexane; and insoluble in octane.
The synthesis of all fluorinated complexes can be
presented by the scheme
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202
DROBOT et al.
Table 1. Crystallographic data and the experimental and refinement parameters for two polymorphous modifications
(from acetone) and b (from alcohol) of complex I
a
Value
Parameter
Ia
Ib
FW
1004.70
1004.70
Space group
C
2/c
P21/n
a
, Å
, Å
, Å
42.357(2)
10.4898(6)
18.4349(10)
106.851(1)
7839.3(8)
1.703
12.6176(9)
23.9022(17)
13.4285(10)
107.490(1)
3862.7(5)
1.728
b
c
β
, deg
V
, Å3
ρcalcd, g/cm3
Z
8
4
F(000)
3952
1976
Crystal size, mm
0.20
×
0.20
×
0.02
0.24
×
0.20 × 0.18
μ
, mm–1
3.385
3.435
θ
range, deg
2.01–27.94
41820/9368/0.056
7170
1.80–28.00
42155/9300/0.053
7930
Number of measured/independent reflections/Rint
Number of reflections with
Range of indices
I > 2σ(I)
–55
–13
–24
≤
≤
≤
h
k
l
≤
≤
≤
55
13
24
–16
–31
–17
≤
≤
≤
h
k
l
≤
≤
16
31
≤
17
Number of parameters
496
496
R
R
factors (
I
> 2
σ
(
I
))
R
1 = 0.042, wR2 = 0.095
1 = 0.065, wR2 = 0.106
1.001
R
1 = 0.029, wR2 = 0.069
1 = 0.038, wR2 = 0.074
1.003
factors (all reflections)
R
R
Goodnessꢀofꢀfit for F2
Δρmax Δρmin
Å3
Tmin Tmax
/
,
e
2.930/–1.660
2.351/–1.496
;
0.551; 0.935
0.493; 0.577
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NEW RHENIUM(III) COMPLEXES WITH FLUORINATED
β
ꢀDIKETONES
203
Table 2. Selected interatomic distances and bond angles for two polymorphous modifications Ia and Ib
Bond
d
, Å
Bond
d
, Å
Bond
d, Å
Ia
Re(1)–O(2)
Re(1)–O(1)
Re(1)–O(3)
Re(1)–Cl(1)
Re(1)–Cl(2)
Re(1)–P(1)
1.972(3)
P(1)–C(18)
P(1)–C(6)
P(1)–C(12)
P(2)–O(3)
P(2)–C(24)
P(2)–C(36)
P(2)–C(30)
1.817(4)
1.821(4)
1.824(4)
1.521(3)
1.776(4)
1.786(4)
1.789(4)
O(1)–C(1)
O(2)–C(3)
C(1)–C(2)
C(1)–C(4)
C(2)–C(3)
C(3)–C(5)
1.287(5)
1.291(5)
1.378(5)
1.525(6)
1.384(6)
1.507(6)
1.986(3)
2.045(3)
2.3518(10)
2.3927(9)
2.4348(10)
Ib
Re(1)–O(2)
Re(1)–O(1)
Re(1)–O(3)
Re(1)–Cl(1)
Re(1)–Cl(2)
Re(1)–P(1)
1.977(2)
1.991(2)
2.042(2)
2.3431(8)
2.3974(8)
2.4387(8)
P(1)–C(18)
P(1)–C(6)
P(1)–C(12)
P(2)–O(3)
P(2)–C(24)
P(2)–C(36)
P(2)–C(30)
1.822(3)
1.821(3)
1.820(3)
1.514(2)
1.793(3)
1.792(3)
1.794(3)
O(1)–C(1)
O(2)–C(3)
C(1)–C(2)
C(1)–C(4)
C(2)–C(3)
C(3)–C(5)
1.288(4)
1.296(4)
1.386(5)
1.515(5)
1.388(5)
1.511(5)
Angle
ω
, deg
Angle
ω
, deg
Angle
ω, deg
Ia
O(2)Re(1)O(1)
O(2)Re(1)O(3)
O(1)Re(1)O(3)
O(2)Re(1)Cl(1)
O(1)Re(1)Cl(1)
O(3)Re(1)Cl(1)
O(2)Re(1)Cl(2)
O(1)Re(1)Cl(2)
O(3)Re(1)Cl(2)
Cl(1)Re(1)Cl(2)
91.34(11)
176.30(11)
85.25(11)
91.31(9)
176.60(8)
92.05(8)
85.99(8)
86.28(8)
92.34(7)
91.78(4)
O(2)Re(1)P(1)
O(1)Re(1)P(1)
O(3)Re(1)P(1)
Cl(1)Re(1)P(1)
Cl(2)Re(1)P(1)
C(18)P(1)Re(1)
C(6)P(1)Re(1)
C(12)P(1)Re(1)
O(3)P(2)C(24)
O(3)P(2)C(36)
O(3)P(2)C(30)
89.75(8)
93.41(8)
C(1)O(1)Re(1)
C(3)O(2)Re(1)
P(2)O(3)Re(1)
O(1)C(1)C(2)
O(1)C(1)C(4)
C(2)C(1)C(4)
C(1)C(2)C(3)
O(2)C(3)C(2)
O(2)C(3)C(5)
C(2)C(3)C(5)
124.5(2)
125.2(3)
152.16(17)
127.9(4)
111.7(3)
120.4(4)
122.8(4)
127.3(4)
112.6(4)
120.0(4)
91.89(7)
88.73(4)
175.72(3)
109.47(13)
114.86(13)
116.77(14)
114.02(17)
109.51(16)
108.46(17)
Ib
O(2)Re(1)O(1)
O(2)Re(1)O(3)
O(1)Re(1)O(3)
O(2)Re(1)Cl(1)
O(1)Re(1)Cl(1)
O(3)Re(1)Cl(1)
O(2)Re(1)Cl(2)
O(1)Re(1)Cl(2)
O(3)Re(1)Cl(2)
Cl(1)Re(1)Cl(2)
91.57(9)
174.58(9)
83.12(9)
93.35(7)
174.75(7)
91.99(7)
89.04(6)
87.50(7)
91.80(6)
90.77(3)
O(2)Re(1)P(1)
O(1)Re(1)P(1)
O(3)Re(1)P(1)
Cl(1)Re(1)P(1)
Cl(2)Re(1)P(1)
C(18)P(1)Re(1)
C(6)P(1)Re(1)
C(12)P(1)Re(1)
O(3)P(2)C(24)
O(3)P(2)C(36)
O(3)P(2)C(30)
87.30(6)
93.16(7)
C(1)O(1)Re(1)
C(3)O(2)Re(1)
P(2)O(3)Re(1)
O(1)C(1)C(2)
O(1)C(1)C(4)
C(2)C(1)C(4)
C(1)C(2)C(3)
O(2)C(3)C(2)
O(2)C(3)C(5)
C(2)C(3)C(5)
125.5(2)
124.6(2)
147.15(14)
126.7(3)
112.5(3)
120.8(3)
123.3(3)
127.9(3)
111.8(3)
120.3(3)
91.91(6)
88.89(3)
176.29(3)
109.85(11)
114.02(11)
117.73(11)
114.30(14)
107.76(14)
110.19(14)
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DROBOT et al.
C(27)
C(28)
C(26)
C(29)
C(25)
F(2)
F(3)
Cl(2)
C(24)
C(37)
C(4)
C(1)
F(1)
C(2)
C(38)
C(30)
C(31)
F(4)
P(2)
C(32)
C(33)
O(1)
O(3)
F(6)
C(36)
Re(1)
C(39)
C(3)
C(41)
C(35)
C(8)
C(5)
C(34)
O(2)
C(20)
C(40)
C(19)
C(18)
Cl(1)
F(5)
C(21)
P(1)
C(7)
C(6)
C(22)
C(17)
C(23)
C(12)
C(11)
C(9)
C(10)
C(16)
C(13)
C(15)
C(14)
Fig. 1. Molecular structure of complex Ia
.
Two polymorphous modifications were found for
complex RF = CF3: modification (well soluble in
ethanol) and modification (moderately soluble in
ethanol). Modifications and were obtained by crysꢀ
tallization from different solvents ( and were crysꢀ
RF
I
a
Cl
(V)
(Ph3P)2
O
H
O
b
+
Re
H
O
a
b
a
b
Cl
OEt
tallized from acetone and ethanol, respectively).
RF
RF
Cl
In the both structures (Figs. 1, 2), the rhenium
atom has a distorted octahedral environment with the
O
(III)
Re(PPh3)(OPPh3)
T, C H , 15–20 min
6 6
H
O
Table 3. Thermal characteristics of complexes I–V
RF
Cl
Td5%
,
°
C
mres, %
RF = CF3(
I
), C2F5(II), C3F7(III), C4F9(IV),
C3F7OCF(CF3) (V).
Comꢀ
pound
Tm, °C Tox, °C
Air Argon Air Argon
A solution of ReОСl2(OC2H5)(PPh3)2 and a small
excess of ꢀdiketone was refluxed in benzene for 15–
β
I
200
194
160
171
155
215
204
178
195
162
235
235
206
235
180
267
249
244
247
177
2
6
46
40
37
29
37
20 min. The compounds began to crystallize after
octane was added to the obtained dark blue solution. It
should be mentioned that we obtained just these comꢀ
plexes containing one triphenylphosphine ligand and
one triphenylphosphine oxide ligand. It can be conꢀ
sidered as established that the reduction of rheꢀ
nium(V) to rhenium(III) is intramolecular due to the
oxidation of triphenylphosphine.
II
III
IV
V
0.5
0
0
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NEW RHENIUM(III) COMPLEXES WITH FLUORINATED
β
ꢀDIKETONES
205
C(27)
C(26)
C(28)
C(25)
F(3)
C(29)
C(24)
C(41)
C(40)
C(35)
Cl(2)
C(4)
C(36)
F(1)
F(2)
P(2)
C(34)
C(33)
C(32)
O(1)
C(1)
C(30)
O(3)
C(39)
C(38)
C(2)
C(31)
Re(1)
F(4)
C(37)
F(6)
C(3)
O(2)
C(20)
C(21)
C(19)
C(5)
Cl(1)
C(11)
P(1)
C(10)
C(6)
F(5)
C(22)
C(18)
C(7)
C(12)
C(9)
C(8)
C(23)
C(13)
C(17)
C(16)
C(14)
C(15)
Fig. 2. Molecular structure of complex Ib
.
same arrangement of the ligands. The chelating perꢀ ments). According to the trans effect described above,
the Re–Clequiv bond is shorter than Re–Claxial
.
fluorinated acetylacetonate, chloride, and coordiꢀ
nated triphenylphosphine oxide ligands form the
equatorial plane of the octahedron, and the
second chloride and coordinated triphenylphosphine
substituents occupy the axial positions. A similar
arrangement of the ligands is explained by their
donor–acceptor properties. It is well known that the
The thermal properties of complexes I–V were
studied by the TG and DTA methods. The correꢀ
sponding curves are presented in Figs. 3 and 4. Some
thermal characteristics are given in Table 3. The 5%
mass loss of the sample was accepted to be the temperꢀ
ature of decomposition onset. The oxidation temperaꢀ
ture was determined as shown in Fig. 3b.
stronger the
stronger ꢀdonor substituent is situated in the trans
position to the ligand (trans effect). Correspondingly,
the strongest donors (triphenylphosphine oxide
σꢀacceptor properties of the ligand, the
σ
The compounds synthesized decompose in several
stages in both air and an inert atmosphere. The onset
of mass loss starts above the melting point of the comꢀ
plexes. When the samples are heated in air, the DTA
curves contain exotherms that appear in the temperaꢀ
ture region of the mass loss onset. The influence of the
σ
and the carbonyl fragment of the chelating acetylaceꢀ
tonate substituent) are localized in front of the stronꢀ
gest σꢀacceptor covalently bound acetylacetonate and
chloride ligands. Although rather strong conjugation is
observed in the acetylacetonate ligand, which is indiꢀ
cated by the alignment of the central C–C and C=C
number n in the fluoroalkyl substituent on the thermal
characteristics of the studied complexes was analyzed.
The curves of the dependences of several thermal
bond lengths, the Re–O (short) and Re
←O (long)
parameters of complexes
length are presented in Fig. 4. It is seen that they pass
through a minimum at = 7 (compound III). For TG
fragꢀ of compounds IV, the temperature of decomposiꢀ
I–IV on the alkyl radical
distances differ, demonstrating the corresponding
character of the fragments of the acetylacetonate subꢀ
n
stituent (σꢀacceptor C–O– or
σ
ꢀdonor C=O
→
I–
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 38
No. 3
2012

206
DROBOT et al.
m
, %
T, °C
100
80
60
40
20
0
(а)
4
3
1
4
5
3
5
240
210
180
Tox
2
3
2
1
300 600
T, °C
2
4
1
0
2
4
n
200
400
600
800
m
, %
T, °C
(b)
Fig. 4. Dependences of the (
temperature, and temperature of decomposition onset
) in air and ( ) in argon on the value of in the fluoroꢀ
alkyl radical.
1) melting point, (2) oxidation
100
(
3
4
n
5
80
60
40
20
0
3
is always lower than that in argon (Table 3). The molꢀ
ecules synthesized contain up to 20% of the metal;
however, heating in air allows one to convert their oxiꢀ
dation products to the vapor phase more than by 94%.
This makes it possible to use the new rhenium comꢀ
1
2
4
plexes with fluorinated
processes.
βꢀdiketones in the MO CVD
200
400
600
T, °C
ACKNOWLEDGMENTS
This work was supported by the Russian Foundaꢀ
tion for Basic Research, project no. 09ꢀ03ꢀ00328.
Fig. 3. (a) TG and DTA curves in air and (b) the TG curves
in argon for complexes ( , ( II, ( III, ( IV, and
at a heating rate of 10°C/min.
1
)
I
2)
3)
4)
(5) V
REFERENCES
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thermal oxidation processes due, most likely, to the
oxidation of the triphenylphosphine groups in the
molecules of ReCl2(RFCOCHCORF)(PPh3)(OPPh3)
and their transformation into triphenylphosphine
oxide followed by the decomposition of the molecules.
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RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 38
No. 3
2012