New stereoselective Csp2-Csp3 coupling: Catalytic iodomethylation of acetylene with methyl iodide into E-1-iodopropene

Article abstract of DOI:10.1134/S0023158414030094

The catalytic addition of methyl iodide to acetylene yielding E-1-iodopropene has been discovered. The reaction competes with the formation of E,E-1,4-diiodobuta-1,3-diene. The key intermediate in these reactions is the methylvinyl derivative of Pt^IV

Full text of DOI:10.1134/S0023158414030094

ISSN 0023ꢀ1584, Kinetics and Catalysis, 2014, Vol. 55, No. 3, pp. 304–310. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © S.A. Mitchenko, O.V. Khazipov, T.V. Krasnyakova, 2014, published in Kinetika i Kataliz, 2014, Vol. 55, No. 3, pp. 319–325.
New Stereoselective
C
2
–
C
3
Coupling:
sp
sp
Catalytic Iodomethylation of Acetylene
with Methyl Iodide into ꢀ1ꢀIodopropene
E
a,
a
a, b
S. A. Mitchenko *, O. V. Khazipov , and T. V. Krasnyakova
a
Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry, National Academy of Sciences of Ukraine,
Donetsk, 83114 Ukraine
Taras Shevchenko National University of Lugansk, Lugansk, 91000 Ukraine
b
*
eꢀmail: samit_RPt@mail.ru
Received September 18, 2013
Abstract—The catalytic addition of methyl iodide to acetylene yielding Eꢀ1ꢀiodopropene has been discovꢀ
ered. The reaction competes with the formation of E,Eꢀ1,4ꢀdiiodobutaꢀ1,3ꢀdiene. The key intermediate in
these reactions is the methylvinyl derivative of PtIV resulting from acetylene iodoplatination by the Pt
Сsp
methyl complex forming in the equilibrium process. The Сsp coupling product in the reductive elimiꢀ
nation of the ligands is ꢀ1ꢀiodopropene. ꢀ1,4ꢀdiiodobutaꢀ1,3ꢀdiene is the product of the iodoplatination
IV
2
–
3
E
E,E
of the second acetylene molecule by this intermediate followed by the Сsp
2
–
Сsp
coupling of the vinyl ligands.
2
DOI: 10.1134/S0023158414030094
INTRODUCTION
thesized in situ by the substitution of the chloride ligands in
the presence of excess NaI in acetoneꢀ 6 solution.
Na PtCl4 was dissolved in a 1.5 M solution of NaI in
d
Catalytic C–C crossꢀcoupling reactions of that
make it possible to obtain complicated compounds
from simpler ones with high efficiency have become an
important tool of contemporary organic chemistry [1,
2
acetoneꢀd6 (0.6 mL), СН3I was added, and the mixꢀ
ture was left standing for 24 h. The resulting sodium
chloride precipitate was separated by centrifugation,
the filtrate was transferred to an NMR ampule, and an
aliquot of a solution of acetylene and NaI (1.5 mol/L)
2
]. Bis(organyl) metal complexes are key intermediꢀ
ates of coupling catalyzed by metal complexes [3]. We
have found recently [4, 5] that the oxidative addition
in acetoneꢀd6 was added.
II
of methyl iodide to Pt iodide complexes followed by
The reactions were carried out at room temperaꢀ
ture and were monitored as the variation of the intenꢀ
the iodoplatination of some substituted alkynes in aceꢀ
tone solution leads to the formation of methylvinyl
1
sity of the corresponding signals in the H NMR specꢀ
IV
derivatives of Pt , which are more stable to C–C couꢀ
trum. The concentrations of acetylene, methyl iodide,
and products were determined relative to the internal
standard (benzene). The equilibrium concentration of
pling. Evident reasons for the stability of the earlier
synthesized methylvinyl complexes of Pt are the
steric hindrance from the bulky substituents in the
vinyl ligands to the reaction and the bidentate characꢀ
ter [5] of some of the ligands. In this work, it is shown
IV
IV
MePt was calculated using the equilibrium constant
II
for the oxidative addition of MeI to the Pt iodide
complexes, which is 0.017 L/mol [4].
that the catalytic Сsp
2
–
Сsp
coupling occurs in the MeI–
3
The NMR parameters of the reaction products and
II
1
13
Pt –NaI–acetone system to form
when an unsubstituted alkyne (acetylene) is used. The spectra were recorded on Bruker AVANCE 500,
results of our kinetic and mechanistic study of the disꢀ Bruker AVANCE II 600, and Bruker AVANCE II 400
Е
ꢀ1ꢀiodopropene intermediates are listed in Table 1. H and СNMR
covered reaction are presented.
spectrometers (Bruker, Germany).
RESULTS
EXPERIMENTAL
Reaction Kinetics
When PtII and MeI are in excess over acetylene (at
additional purification to prepare solutions. The salt the initial concentration ratios of [Pt ] : [С H ] :
Commercial NaI (reagent grade), methyl iodide
(
Aldrich), and acetoneꢀ 6 (Merck) were used without
d
II
0
2
2 0
Na PtCl was synthesized according to a known proꢀ [MeI]
≈
1 : 0.1 : 15) in acetoneꢀd6 and when there is a
2
4
cedure [6]. The platinum iodide complexes were synꢀ large excess of NaI excess, acetylene consumption is
304

NEW STEREOSELECTIVE
C
2
–
C
3
305
sp
sp
Table 1. NMR parameters for the products and intermediates of the reaction between acetylene and methyl iodide in the
II
C H –MeI–Pt –NaI–acetone system
2
2
1H NMR:
δ
(ppm) and
J
(Hz)
13
C{ H} NMR (
1
δ
, ppm)
Compound
Complex
1
8.18 (d,
J
(H–H) = 13 with satellites 195Pt,
3
H
2–
CH3
2
1
J
(Pt–H) = 51.5; 1H; H ), 5.61 (d,
J(H–H) = 13
I
C 1
2
–
195
3
2
Pt
I
I
with satellites Pt, J(Pt–H) = 39.1; 1H; H ),
C
I
I
195
2
3
3.16 (s with satellites Pt, J(Pt–H) = 76.6; 3H; H )
H
Complex
2
H
8.01 (d,
J
(H–H) = 13 with satellites 195Pt,
3
2–
4
CH3
2
1
J
(Pt–H) = 40.3; 1H; H ), 5.39 (d;
J
(H–H) = 13
1
H C
C
2
–
3
195
3
2
Pt
I
I
with satellites Pt, J (Pt–H) = 44.9; 1H; H ),
C
I
I
195
2
3
4
2.08 (s with satellites Pt, J (Pt–H) = 77.5; 6H; H and H )
H
E
ꢀ1ꢀiodopropene
e2
H
e1
e2
e1
e2
I
6.22 (d,
J
(H–H) = 13; 1H; H ), 6.53 (m, 1H; H ),
75.3 (C ), 141.1 (C ),
e3
e3
1.73 (dd,
J(H–H) = 6.8;
J
(H–H) = 1.6; 3H; H )
18.4 (C )
e3
H C
3
H
e1
E
ꢀbutꢀ2ꢀene
b1
H
b2
CH3
b1
b2
b1
b2
5
.41 (m, 2H, H ); 1.59 (m, 6H, H )
125.2 (C ), 17.3 (C )
H C
H
3
b2
b1
E
,E
ꢀ1,4ꢀdiiodobutaꢀ1,3ꢀdiene
d2
I
H
d1
H
d1
d2
d1
d2
6
.96 (m, 2H, H ); 7.23 (m, 2H, H )
82.3 (C ), 145.9 (C )
H
d1
H
I
d2
E,Eꢀ1ꢀiodopentaꢀ1,3ꢀdiene
t5
t3
t1
t1
t2
H C
3
H
6.43 (d,
J
(H–H) = 14.3, 1H, H ); 7.05 (dd,
J
(H–H) = 14.3; 76.6 (C ), 145.1 (C ),
t1
H
t2
t3
t4
t3
t4
10.3; 1H, H ); 6.15 (m, 1H, H ); 5.84 (m, 1H, H );
131.5 (C ), 130.4 (C ),
t5
t5
H
1.69 (m, 3H, H )
21.1 (C )
t4
H
I
t2
E,Eꢀhexaꢀ2,4ꢀdiene
p3
H C
p2
H
3
p1
H
p1
p2
1
1
25.7 (C ), 131.6 (C ),
p1
p2
p3
5.55 (m, 2H, H ); 6.01 (m, 2H, H ); 1.68 (m, 6H, H )
p3
3.3 (C )
H
p1
H
CH
3
p2
p3
KINETICS AND CATALYSIS Vol. 55
No. 3 2014

306
MITCHENKO et al.
accompanied by the parallel formation of the crossꢀ
coupling product of acetylene and methyl iodide,
–3
Concentration
×
10 , mol/L
namely,
70% yield based on reacted acetylene) and a minor
amount of ꢀ1,4ꢀdiiodobutaꢀ1,3ꢀdiene (dibd,
29% yield based on reacted acetylene)
Еꢀ1ꢀiodopropene as the major product (ip,
5
4
3
2
1
~
E,E
~
2
H
I
H C
3
H
ip
II
–
1
Pt , I
+
.
CH3I
HC CH
(I)
H
I
3
H
I
4
H
H
dibd
0
10
20
30
40
50
Time, h
The presence of both PtII and methyl iodide is necꢀ
essary for these reactions to take place: reactions (I) do
not occur in the absence of at least one of the reacꢀ
tants. In addition to the formation of ip and dibd, the
Fig. 1. Typical kinetics of (
ꢀ1ꢀiodopropene accumulation, (
,3ꢀdiene accumulation, and ( ) complex 1
1
) acetylene disappearance,
ꢀ1,4ꢀdiiodobutaꢀ
accumulation. The
(
1
2
)
E
3) E,E
4
II
initial platinum concentration is [Pt ] = 0.05 mol/L.
0
formation of the intermediate methylvinyl derivative
IV
of Pt (complex 1) (Fig. 1) and the evolution of traces
lene concentration increases and the other conditions
remain unchanged (Table 2, entries 4–6). In this case,
1
of methane were detected by H NMR spectroscopy.
The acetylene disappearance kinetics obeys a firstꢀ
order equation. The apparent pseudoꢀfirstꢀorder rate
the formation of another organoplatinum intermediꢀ
1
ate (complex
copy.
2
) was detected by H NMR spectrosꢀ
constant
of
acetylene
, increases with an increasing conꢀ
centration of PtII or methyl iodide (Table 2). The dibd formations: ip gives
disappearance,
d ln[C H ]
2
2
kapp = −
Then the primary products undergo slower transꢀ
ꢀbutꢀ2ꢀene, and dibd produces
dt
E
yield increases, the ip yield decreases, and kapp
E,Eꢀ1ꢀiodopentaꢀ1,3ꢀdiene, which then transforms
increases approximately two times as the initial acetyꢀ into ꢀhexaꢀ2,4ꢀdiene:
E,E
H
I
H
CH3
H
CH3I
PtII
,
H C
3
H
H C
3
(II)
H
CH3
H
H
CH3
H
H
I
CH3I
PtII
CH3I
PtII
H
I
H
H
I
.
H
H
H3C
H
H
II
For example, 30 h after the beginning of the reaction,
under the conditions indicated in Table 2 (entry 6),
At initial concentrations of [Pt ] = 0.01, [С H ]
2 0
=
0
2
0
.32, and [MeI]0 = 1.3 mol/L, the concentration of the
resulting ꢀ1ꢀiodopropene in 20 days is 0.034 mol/L,
which indicates the catalytic character of the reaction
and corresponds to a turnover number of 3.4.
Е
9
0% of the acetylene is reacted,
mulated in trace amounts, and the yields of
iodopentaꢀ1,3ꢀdiene, ꢀhexaꢀ2,4ꢀdiene, and dibd
are (19 2), (4 ), and (58 )%, respectively, based
Е
ꢀbutꢀ2ꢀene is accuꢀ
E,Eꢀ1ꢀ
E,E
±
±
1
±
6
on reacted acetylene. Fot this reason, the yields of ip
and dibd in Table 2 are extrapolated to the onset of the
reaction, when the formation of secondary products
Identification of the Products and Intermediates
of Reactions (I) and (II)
Complexes 1 and 2. The fairly large value of the
increases spin–spin coupling constant
J(H–H) (Table 1) indiꢀ
can be neglected. The yield ratio
ηdibd/
η
ip
1
linearly with an increasing initial acetylene concentraꢀ cates the trans arrangement of the vinyl protons H
2
tion (Fig. 2).
and H (for the numbering of atoms, see Table 1). The
KINETICS AND CATALYSIS Vol. 55
No. 3 2014

NEW STEREOSELECTIVE
C
2
–
C
3
307
sp
sp
Table 2. Apparent pseudoꢀfirstꢀorder rate constant kapp and the yields of the products extrapolated to the onset of the reꢀ
action as a function of the initial concentrations of acetylene, methyl iodide, and Pt
II
II
[
Pt ]
[MeI]0
mol/L
[C H ]
η
ip
η
dibd
0
2
2 0
Entry
kapp, h–1
%
1
2
3
4
5
6
7
8
0
1.3
0
0.13
0
0
0
0
0.05
0.1
0
–
0.015
0.05
0.05
0.05
0.1
0.68
1.0
1.0
1.0
0.9
1.3
0.13
18 ± 3
70 ± 6
51 ± 5
26 ± 2
81 ± 6
75 ± 6
75 ± 8
29 ± 3
56 ± 6
73 ± 6
19 ± 4
18 ± 3
0.010 ± 0.002
0.048 ± 0.005
0.06 ± 0.01
0.07 ± 0.01
0.055 ± 0.005
0.095 ± 0.01
0.0056
0.027
0.1
0.0016
0.002
0.11
1
positions of H signals and the value of
characteristic of protons at the С sp atom bound to
platinum through a bond [4, 5, 7]. The position of the
J
(Pt–H) are
E,EꢀHexaꢀ2,4ꢀdiene. Use of the 2D COSY techꢀ
nique makes it possible to reveal the spinꢀspin couꢀ
pling between the p1 and p2 protons and between
2
σ
them and the p3 protons of the methyl groups. The
3
3,4
Н
(complex
1
) and
(Pt–H) correspond to the methyl ligands of
, the integral
Н
(complex
2
) signals and the
p3
radiation damping of the
Н signal makes the multiꢀ
values of
J
plicity of the 1
Н
NMR spectrum similar to the multiꢀ
IV
the Pt derivatives [7]. For complex
1
plicity of the signal from dibd. The radiation damping
1
2
3
р1
р2
р3
intensity ratio is Н : Н : Н = 1 : 1 : 3, which correꢀ
sponds to the organoplatinum derivative including the
vinyl and methyl ligands. Due to their equivalence, the
protons of methyl groups 3 and 4 of complex
H NMR spectrum form a single signal, and, as a conꢀ the
of the
Н signal makes the Н and Н signals degenꢀ
р2
erate into singlets. The radiation damping of the
signal results in the degeneration of the
Н
р1
Н signal into
2
in the
a quadruplet with = 6 Hz and in the degeneration of
J
1
р3
Н
signal into a doublet with the same value of
J.
1
2
3,4
13
1
sequence, the ratio of signal intensities is H : H : H = The C{ H} NMR spectrum is in agreement with the
: 1 : 6. The concentrations of complexes and
were literature [8].
insufficient for C and Pt NMR experiments, so the
The signals of
1
1
2
1
3
195
Еꢀbutꢀ2ꢀene and dibd were assigned
r
structures of these complexes were deduced from thei according to earlier published data [9, 10].
H NMR spectra.
1
1
E
ꢀ1ꢀiodopropene. The H NMR signal at 1.73 ppm
is split into a doublet of doublets with
.8 Hz. The signal at 6.53 ppm is a complicated mulꢀ
tiplet, and the signal at 6.22 ppm is split into a doublet
of quadruplets with = 14.3 and 1.6 Hz. The spin–
spin coupling between Н , Н , and
J = 1.6 and
6
J
e1
e2
е3
Н
shows itself as
η
dibd/
η
ip
cross peaks in the 2D COSY spectrum, indicating that
these protons belong to one molecule. The radiation
damping of the signal at 1.73 ppm results in the degenꢀ
eration of the two multiplets at 6.53 and 6.22 ppm into
5
4
3
2
1
doublets with
teristic of the trans arrangement of the H and H
protons. The radiation damping of the H signal
reduces the multiplicity of the H signal: the doublet
J = 14.3 Hz. The latter value is characꢀ
e1
e2
e1
e2
of quadruplets degenerates into a quadruplet.
E,Eꢀ1ꢀIodopentaꢀ1,3ꢀdiene. In the 2D COSY
spectrum, the t1 proton shows spin–spin coupling
with the t2 proton; as a result, its signal is split into a
doublet with a large coupling constant of
J = 14.3 Hz,
t1
which is characteristic of the trans arrangement of
Н
t2
t1
t3
0
0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16
[C H ], mol/L
and
Н . The t2 proton is coupled with Н and Н ,
1
and, accordingly, its signal in the H NMR spectrum is
2
2
split into a doublet of doublets. The 2D COSY specꢀ
Fig. 2. Ratio of the yields of dibd and ip extrapolated to the
onset of the reaction as a function of the initial acetylene
concentration.
t3
trum indicates spin–spin coupling between the
Н
t4
t4
t5
proton and
Н and between H and H .
KINETICS AND CATALYSIS Vol. 55
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308
MITCHENKO et al.
2–
I
H C
H
I
I
3
Pt
H
I
I
ip
HC CH, I–
1
3
CH3I
I–
k
K
3
1
4
k
4
H
H
2–
CH3
I
C
C
I
2–
2
–
Pt
H
I
CH3
Pt
CH3
I
I
I H
H
C
I
I
I
I
I
complex
3
Pt
I
H
I
complex
1
I
5
k
5
I
k
2
I
I
2
dibd
–
2
HC CH, I–
I
CH3
Pt
I
I
Scheme 1
.
Stepwise mechanism of the formation of ip and dibd.
DISCUSSION
The observed effects can be explained in terms of
pseudoꢀfirstꢀorder rate constant is kapp
≈
a and 2a in
two limiting cases of (low initial concentration
β
ӷ
2
of acetylene) and 2 (high initial concentration of
β
Ӷ
the stepwise mechanism presented in Scheme 1. The
acetylene), respectively. At medium values of the iniꢀ
tial concentration, acetylene is consumed at the interꢀ
mediate rate exp(−2at) < x < exp(−at), but, in the
strict sense, its disappearance kinetics does not obey a
firstꢀorder equation. Nevertheless, this kinetics can be
approximated [11] by a firstꢀorder equation with an apparꢀ
II
oxidative addition of CH3I to Pt is reversible and
IV
yields a Pt methyl derivative [4] (step 1), which is the
active form of the catalyst. The iodoplatination of the
С С bond of acetylene by the latter (step 2) results in
≡
IV
the formation of an intermediate Pt methylvinyl
derivative (complex ), whose decomposition via
Сsp
reductive elimination gives the Сsp crossꢀcouꢀ
1
ent rate constant satisfying the inequality
Thus, the experimentally observed twofold
a < kapp < 2a.
2
–
3
pling product (ip) and regenerates the catalyst (step 3). increase in kapp as a result of an increase in the iniꢀ
The iodoplatination of the second acetylene molecule tial concentration of the substrate (Table 2, entries 4–6)
by complex
1 with the intermediate formation of the can be explained in the framework of Scheme 1.
methyldivinyl derivative (step 4) followed by fast
reductive elimination affords dibd. A similar iodoꢀ
platination of alkyne by the Pt methylvinyl complex tion is given by the equation
under the same conditions, accompanied by methꢀ
yldivinyl derivative formation, was observed for
methyl propionate [4].
According to Scheme 1, the ratio of the yields of
dibd and ip extrapolated to the onset point of the reacꢀ
IV
η
dibd
k4
≈
[C H ] ,
(2)
2
2 0
η
ip
k3
In the framework of Scheme 1, in a large excess of which is consistent with the experimental results
methyl iodide and under the quasiꢀsteadyꢀstate condiꢀ
tions with respect to intermediate complex , the acetꢀ
ylene disappearance kinetics is described by the equaꢀ
tion
k4
(
Fig. 2) at
= (29 ± 2) L/mol. The value obtained
1
k
3
makes it possible to estimate the lower limit of the ratio
of the rate constants of Сsp
plings ( 5 k3). No formation of a noticeable concenꢀ
tration of the Pt methyldivinyl derivative (complex
was detected at the maximum acetylene concentration
used in this work (0.13 mol/L). This means that, under
the given conditions, the steadyꢀstate concentration of
this derivative is substantially lower than the steadyꢀ
state concentration of complex
k5 and, hence, k5 . The validity of Eq. (2) indiꢀ
cates that ip forms predominantly in step 3. Therefore,
2
–
Сsp
2
and Сsp
2
–
Сsp
couꢀ
3
k
/
x
=
exp(−at),
(1)
IV
3)
β + 2x
β + 2
[
C H ]
2 2
where x =
is the fraction of acetylene that has
[C H ]
2 2 0
1. Therefore, 0.13 k4
Ӷ
k3
not reacted by the time
t,
β =
, and a =
k3
ӷ
/ 4
k [C H ]
2 0
4
2
II
k2K1[Pt ][MeI]. Equation (1) shows that the apparent reductive elimination during the decomposition of
KINETICS AND CATALYSIS Vol. 55
No. 3 2014

NEW STEREOSELECTIVE
C
2
–
C
3
309
sp
sp
H C
H
I
3
H
ip
2–
6
H
CH3
I
C
CH3
–
–
CH + OH + PtI
3
Pt
4
H
I
I
H O
2
I
1
complex
2
2–
2–
CH3
Pt
I
CH3
I
O2
2
I
I
I
Pt
I
I
5
I
VinI
3
HC CH, I–
4
CH3I
2–
–
CH3
Pt
CH3
I
I
Vin
I
I
CH3
I
Pt
I
I–
I
7
H
H
I
H
CH3
H
2–
H
H
I
I
I
I
Vin =
,
,
,
H
H
Pt
+ VinCH3
H C
H
3
H
Scheme 2. Possible transformation routesof the methyl derivative of PtII.
couꢀ lower electrophilicity of the methyl derivative of PtIV
Сsp
complex
3
with the formation of the Сsp
2
–
2
2
−
pling product occurs much more readily than of compared to that of PtI .
6
the elimination yielding the Сsp
product, which agrees with earlier published data [12, 13]. (Scheme 1, steps 2, 4) involve the trans
of platinum and iodine atoms to the triple bond of
acetylene with the formation of ꢀiodovinyl derivaꢀ
2
–
Сsp
3
coupling
Note that the acetylene iodoplatination steps
anti) addition
(
In the experiments where ip was the main product
Table 2, entries 4, 7, 8), 2 and, hence,
ӷ
E
(
β
tives of platinum(IV) only. The stereoselectivity of
iodoplatination is usually attributed [15, 16] to the
polarity of the solvent used: the Eꢀconformers form in
kapp
≈
k2[MePtIV],
(3)
IV
II
where [MePt ] =
K
1
[Pt ][MeI] is the equilibrium
concentration of the PtIV methyl complex. Indeed, the polar solvents, including acetone. The insertion of
experiments demonstrate a linear dependence of the acetylene into the Pt–I bond with the formation of the
apparent pseudoꢀfirstꢀorder rate constant on the equiꢀ cis (syn) addition product is lowꢀsensitive to solvent
IV
librium concentration of the Pt methyl complex polarity and can occur in lowꢀpolar and nonpolar solꢀ
(
Fig. 3). The validity of dependence (3) is consistent vents.
IV
The subsequent transformations of the PtII methyl
with the assumption that the Pt methyl complex parꢀ
ticipates in step 2 of acetylene iodoplatination. The derivative formed in step 5 (Scheme 1) elucidate the
secondꢀorder rate constant determined from the slope of routes of the formation of the experimentally observed
the plot of kapp versus the equilibrium concentration of the secondary reaction products (Scheme 2).
IV
–1 –1
Pt methyl complex is k2 = (0.012
±
0.001) L mol s .
The protolysis of MePtII (step 1) under the action
of water traces can be responsible for methane formaꢀ
This value is close in its order of magnitude to the rate
2
−
constant of acetylene iodoplatination by PtI6 in methaꢀ tion. The oxidative addition of the organoiodine comꢀ
–1
–1
II
nol solution at 40
°
C
, which is 0.040
±
0.003 L mol s
pounds to MePt should afford bis(organyl) derivaꢀ
IV
[
14]. The somewhat smaller value of k2 obtained in the tives of Pt (steps 3, 4). The iodoplatination of acetyꢀ
present work can be a consequence of the lower temꢀ lene by the Pt dimethyl complex (step 5) is for the
IV
perature of reaction (I), the solvent effect, and/or the cause of the formation of experimentally observed
KINETICS AND CATALYSIS Vol. 55
No. 3 2014

310
MITCHENKO et al.
2. Beletskaya, I.P. and Cheprakov, A.V., in
kapp, h–1
Comprehensive
Coordination Chemistry II, Amsterdam: Elsevier, 2004,
vol. 9, p. 305.
0
0
0
0
0
.10
.08
.06
.04
.02
3
.
MetalꢀCatalyzed CrossꢀCoupling Reactions, Diederich, F.
and Stang, P.J., Eds., Weinheim: WileyꢀVCH, 1998,
p. 1.
. Mitchenko, S.A., Khazipov, O.V., and Krasnyakova, T.V.,
Theor. Exp. Chem., 2012, vol. 48, no. 4, p. 246.
4
5
. Mitchenko, S.A., Khazipov, O.V., Zubritskii, M.Yu.,
Krasnyakova, T.V., and Silina, N.S., Theor. Exp. Chem.
012, vol. 48, no. 5, p. 338.
,
2
6.
Sintez kompleksnykh soedinenii metallov platinovoi
gruppy: Spravochnik (Synthesis of Platinum Group
Metal Complexes: A Handbook), Chernyaev, I.N., Ed.,
Moscow: Nauka, 1964.
. Priqueler, J.R.L., Butler, I.S., and Rochon, F.D., Appl.
Spectrosc. Rev., 2006, vol. 41, no. 3, p. 185.
. Hasegawa, K.ꢀI., Asami, R., Takahashi, K., Bull. Chem.
Soc. Jpn., 1978, vol. 51, p. 916.
. Harris, R.K. and Howes, B.R., J. Mol. Spectrosc., 1968,
0
0.5
1.0
1.5
2.0
7
8
9
IV
MePt ] ×
103, mol/L
[
Fig. 3. Apparent pseudoꢀfirstꢀorder rate constant for aceItVꢀ
ylene disappearance as a function of the equilibrium MePt
concentration.
vol. 28, p. 191.
1
1
1
0. Mitchenko, S.A., Ananikov, V.P., Beletskaya, I.P., and
Ustynyuk, Y.A., Mendeleev Commun., 1997, vol. 7,
no. 4, p. 130.
1. Mitchenko, R.S., Krasnyakova, T.V., Zhikharev, I.V.,
and Mitchenko, S.A., Theor. Exp. Chem., 2012, vol. 48,
no. 3, p. 157.
complex
2
, which can decompose via Сsp
2
–
Сsp
couꢀ
3
pling (step 6), regenerating MePtII and providing an
additional route for ip formation. More complicated
Сsp
2
Сsp
– coupling products can form via reductive
3
2. Ananikov, V.P., Musaev, D.G., and Morokuma, K.,
elimination from the methylvinyl derivatives (step 7).
II
Organometallics, 2005, vol. 24, p. 715.
The Pt methyl derivative can also be oxidized [17]
IV
13. Ariafard, A., Ejehi, Z., Sadrara, H., Mehrabi, T.,
Etaati, S., Moradzadeh, A., Moshtaghi, M., Nosrati, H.,
Brookes, N.J., and Yates, B.F., Organometallics, 2011,
vol. 30, p. 422.
with atmospheric oxygen to MePt (step 2).
ACKNOWLEGMENTS
14. Mitchenko, S.A., Kinet. Catal., 1999, vol. 40, no. 2,
This work was supported by the National Academy
p. 248.
of Sciences of Ukraine (grant no. 0111U009945). We 15. Ananikov, V.P., Musaev, D.G., and Morokuma, K.,
are sincerely grateful to V.P. Ananikov, Corresponding
Organometallics, 2001, vol. 20, p. 1652.
Member of the Russian Academy of Sciences, for givꢀ 16. Ananikov, V.P., Kashin, A.S., Hazipov, O.V.,
ing us the opportunity of recording NMR spectra.
Beletskaya, I.P., and Starikova, Z.A., Synlett, 2011,
vol. 2011, p. 2021.
1
7. Vedernikov, A.N., Chem. Commun., 2009, vol. 32,
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Translated by E. Yablonskaya
KINETICS AND CATALYSIS Vol. 55
No. 3 2014