5
52
AGEEVA et al.
The kinetic parameters were calculated by the non-
linear regression technique using SigmaPlot program.
δ, ppm: in CDCl
(NCH ), 3.87 m (CH), 6.74–7.24 m (3-H, 4-H, 5-H,
6-H); in CDCl –pyridine-d : 1.64 d (CCH ), 2.75 s
and 2.97 s (NCH ), 3.85 m (CH), 5.97 d.d (6-H), 6.73–
6.96 m (3-H, 4-H, 5-H).
3
: 1.59 d (CCH ), 2.65 s and 2.92 s
3
3
The apparent pseudofirst-order rate constants k were
3
5
3
ap
calculated from the kinetic curve using the following
equation:
3
D
τ
= D
∞
+ (D
o
– D
∞
)exp(–kapτ).
REFERENCES
Here, D , D , and D are the optical densities at
τ
∞
0
1. Kurzeev, S.A., Kazankov, G.M., and Ryabov, A.D.,
a moment τ, by the end of the process, and in the initial
moment, respectively. The kinetic curves are described
by first-order equation for at least 5 half-conversion
periods. From the dependence of the apparent rate con-
stants on the concentration of palladium complexes we
Russ. J. Org. Chem., 2000, vol. 36, p. 1330.
. Kurzeev, S.A., Kazankov, G.M., and Ryabov, A.D.,
Inorg. Chim. Acta, 2000, vol. 305, p. 1.
. Kurzeev, S.A., Kazankov, G.M., and Ryabov, A.D.,
2
3
J. Inorg. Biochem., 2001, vol. 86, p. 304.
calculated the catalytic hydrolysis rate constants k by
cat
4. Ryabov, A.D., Kazankov, G.M., Kurzeev, S.A., Samu-
leev, P.V., and Polyakov, V.A., Inorg. Chim. Acta, 1998,
vol. 280, p. 57.
5. Ryabov, A.D., Kazankov, G.M., Yatsimirsky, A.K.,
Kuz’mina, L.G., Burtseva, O.Y., Dvortsova, N.V., and
Polyakov, V.A., Inorg. Chem., 1992, vol. 31, p. 3083.
the formula k = k + k [Pd(II)], where k is the rate
ap
0
cat
0
constant of hydrolysis in the absence of catalyst, and
Pd(II)] is the initial concentration of the palladium
complex (calculated on the monomeric species).
R)- and (S)-Chloro(1-phenylethanamine-C,N)-
pyridine)palladium(II) (I). The stereoisomeric com-
[
(
6
. Schmulling, M., Ryabov, A.D., and van Eldik, R.,
(
J. Chem. Soc., Dalton Trans., 1994, p. 1257.
plexes were synthesized according to the procedure
described in [4] from di-μ-chlorobis(1-phenylethan-
amine-C,N)dipalladium(II) [17]. R Isomer: yield 91%,
7
. Schmulling, M., Grove, D.M., van Koten, G., van El-
dik, R., Veldman, N., and Spek, A.L., Organometallics,
1996, vol. 15, p. 1384.
2
0
[
9
α] = –24.3° (c = 0.85%, CHCl ); S isomer: yield
D
3
2
0
1
8. Calmes, M., Glot, C., Michel, T., Rolland, M., and Mar-
7% [α] = +23.8° (c = 0.72%, CHCl ). H NMR
D 3
tinez, J., Tetrahedron: Asymmetry, 2000, vol. 11, p. 737.
spectrum (CDCl ), δ, ppm: 1.63 d (CCH , J = 6 Hz),
3
3
9
. Scrimin, P., Tecilla, P., and Tonellato, U., J. Org. Chem.,
994, vol. 59, p. 4194.
3
.40 and 4.70 br.d (NH ), 4.44 q (CH, J = 6 Hz), 6.13 d
2
1
(
6-H, J = 8 Hz), 6.81 t (5-H, J = 8 Hz), 6.87 d (3-H,
J = 8 Hz), 7.02 t (4-H, J = 8 Hz), 7.75 t (γ-H, J =
Hz), 8.67 d (α-H, J = 7 Hz); the signal from β-H in
the pyridine ring was obscured by the solvent signal.
R)- and (S)-Di(μ-chloro)bis(N-methyl-1-phenyl-
1
0. Cleijg, M.C., Mancins, F., Scrimin, P., Tecillag, P., and
Tonellato, U., Tetrahedron, 1997, vol. 53, p. 357.
1. Pellissier, H., Tetrahedron, 2003, vol. 59, p. 8291.
2. Cran, A.G., Gibson, C.L., and Handa, S., Tetrahedron:
Asymmetry, 1995, vol. 6, p. 1553.
3. Bassas, O., Llor, N., Santos, M.M.M., Griera, R.,
Molins, E., Amat, M., and Bosch, J., Org. Lett., 2005,
vol. 7, p. 2817.
7
1
1
(
ethanamine-C,N)dipalladium(II) (II). The stereoiso-
meric complexes were synthesized from di-μ-acetobis-
1
(
[
N-methyl-1-phenylethanamine-C,N)dipalladium(II)
18] and sodium chloride according to the procedure
1
4. Jitsukawa, K., Katoh, A., Funato, K., Ohata, N., Funa-
for bridging ligand exchange [18–20]. R Isomer: yield
hashi, Y., Ozawa, T., and Masuda, H., Inorg. Chem.,
2
0
7
0%, [α] = –99° (c = 0.77%, CH CN); S isomer:
D 3
2
003, vol. 42, p. 6163.
20
1
yield 74%, [α] = +109° (c = 0.71%, CH CN). H NMR
D
3
1
1
1
5. Makino, K., Goto, T., Hiroki, Y., and Hamada, Y.,
Angew. Chem., Int. Ed., 2004, vol. 43, p. 882.
6. Dunina, V.V., Golovan, E.B., and Gulyukina, N.S.,
Tetrahedron: Asymmetry, 1995, p. 2731.
7. Ryabov, A.D., Polyakov, V.A., and Yatsimirsky, A.K.,
spectrum (CDCl ), δ, ppm: 1.60 d (CCH , S ), 1.72 d
3
3
N
(
CCH , R ), 2.65 d (NCH , S ), 2.89 d (NCH , R ),
3 N 3 N 3 N
3
5
6
.42 m (CH, S ), 3.90 m (CH, R ), 5.18 br.d (NH, S ),
N N N
.40 br.d (NH, R ), 6.04 d (3-H, S ), 6.10 d (3-H, R ),
N
N
N
.78 d.d (6-H), 6.89–6.98 m (4-H, 5-H).
J. Chem. Soc., Perkin Trans. 2, 1983, p. 1503.
(
R)- and (S)-Di(μ-chloro)bis(N,N-dimethyl-1-
18. Fuchita, Y., Tsuchiya, H., and Miyafuji, A., Inorg. Chim.
Acta, 1995, vol. 233, p. 91.
phenylethanamine-C,N)dipalladium(II) (III). The
complexes were synthesized according to the proce-
dure described in [4] from K PdCl and N,N-dimethyl-
1
9. Fuchita, Y., Yoshimura, Y., Hagino, Y., Kawano, H.,
and Kinoshita-Nagaoka, J., J. Organomet. Chem., 1999,
vol. 580, p. 273.
2
4
2
0
1
-phenylethanamine. R Isomer: yield 86%, [α] =
D
+
57.3° (c = 1.85%, CHCl ); S isomer: yield 83%,
D 3
20. Vicente, J., Saura-Llamas, I., and Palin, G., Organo-
metallics, 1997, vol. 16, p. 826.
3
20
1
[
α] = –42.8° (c = 0.71%, CHCl ). H NMR spectrum,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 4 2007