1446
BICHAN et al.
EXPERIMENTAL
2,3,7,8,12,13,17,18ꢀOctaethylporphinato)(oxo)(pheꢀ
1H NMR (CDCl3),
.36 (m, 16H, CH ), 10.94 (m, 2H, meso).
δ
, ppm: 2.13 (m, 24H, CH ),
3
4
2
(
1
1
H– H 2D COSY NMR (CDCl ), , ppm: 4.36
δ
noxo)rhenium(V) O=Re(OPh)OEP (1). H OEP and
3
2
(
m, 16H, СH2)–2.13 (m, 24H, СH3).
H ReCl6 in 1 : 5 molar ratio were refluxed in phenol at
54 K for 9 h. Completion of the complex formation
2
4
(5,15ꢀDiphenylꢀ2,3,7,8,12,13,17,18ꢀoctaethylpoꢀ
5,15
reaction was detected by spectrophotometry. The rphinato)(oxo)(chloro)rhenium(V), O=Re(Cl) DPOEP
reaction mixture was transferred into CH Cl2, the (3). The synthesis and isolation procedures were simiꢀ
2
resulting solution was washed many times by warm lar to the procedure presented above for compound
1
5
2
,15
water to remove phenol, concentrated, and chromatoꢀ
graphed on an Al O column (Brockmann activity II)
with
H
DPOEP being used instead of H OEP. The
2
2
3
synthesis time was 6 h. Chloroform served as the eluꢀ
ent for chromatography. The yield was 75%.
using CH Cl as the eluent. This gave two zones, a pink
2
2
zone containing H OEP and a greenꢀbrown zone. The
2
UVꢀVis (CH Cl ),
λ
max, nm (log ): 625 (3.70), 525
ε
2
2
substance of the second zone was once again chromatoꢀ
graphed on a silica gel column (40/100 Chemapol). Eluꢀ
tion with benzene produced two zones, a pale orange
impurity zone and a greenꢀbrown zone of the target
complex strongly retained at the start. The complex
zone was eluted with a CH Cl –C H OH mixture (1 :
(
4.15), 354 (4.75).
–
1
IR (KBr),
(C–H)); 1600, 1532, 1491 (
C–H); 702, 742 ( (C–H)); pyrrole groups, 1465
(C=N)), 1384 ( (C–N)), 1062 (C –C , (C–N)
(C–H)); methine groups,
(C–H)); 838, 861 ( (C–H)); coordination
center, 962 (Re=O), 467 (Re–N).
1H NMR (CDCl3),
, ppm, , Hz: 1.56 (br. s, 14H,
ν, cm : phenyl groups, 3059, 3022
(
(
(
ν
δ
ν
ν
(C=C)); 1125, 1073
γ
ν
ν
;
3
4
2
2
2
5
alkyl groups, 1400, 1341 (
δ
1
v/v), and the resulting solution was again chromatoꢀ
1
274 (
δ
γ
graphed on a silica gel column (40/100 Chemapol)
using dichloromethane as the eluent. This gave
O=Re(OPh)OEP in 70% yield.
δ
J
CH3), 1.95 (t, 10H, CH ), 2.70 (br.s, 6H, CH ), 4.20
3
2
UVꢀVis (CH Cl ),
λmax, nm: 613 sh, 580, 469, 343;
2
2
(
J
J
m, 10 H, CH ), 7.55 (q, 1Hp,
J
= 7.3); 7.73 (q, 1Hp,
2
(
AcOH): 634 sh, 597, 490, 341.
= 7.3), 7.85 (
m, 2H ), 7.91 (m, 2H ), 8.20 (d, 2H ,
m m o
–
1
IR (KBr),
ν
, cm : pyrrole rings, 1468 (
(C–N)); alkyl
(C–H)), methine groups, 1273, 1223
(C–H)), 873, 844, ( (C–H)); coordination center,
59 (Re=O), 454, 466 (Re–N), 670 (Re–O); axial
ν
(C=N)),
= 8.1), 8.29 (d, 2H ,
J
= 8.1), 10.82 (m, 2H, meso).
H– H 2D COSY NMR (CDCl ), , ppm, , Hz:
.70 (br.s, 6H, CH )–1.95 (t, 10H, CH ); 4.20 (m,
o
1
376 ( (C–N)), 1057 (C –C ,
ν
ν
1
1
3
4
δ
J
3
groups, 1317 (
δ
2
1
2
3
(
9
δ
γ
0H, CH )–1.56 (br.s, 14H, CH ); 4.20 (m, 10H,
2
3
CH )–1.95 (t, 10 H, CH ); 7.85 (m, 2H )–7.55 (q,
2
3
m
ligand, 1589, 1451 (–Ph).
1
Hp,
J
= 7.3); 7.91 (m, 2H )–7.73 (q, 1H ,
J
= 7.3);
, ppm: 1.83 (m, CH ), 4.03 (m, 8.20 (d, 2Ho, J = 8.0)–7.85 (m, 2H ); 8.29 (d, 2H ,
3
m
p
1H NMR (C D6),
δ
6
m
o
1
1
(
6 H, CH ), 4.43 (m, 32 H, CH ), 9.51 (m, 8H, meso),
J
= 8.1)–7.91 (m, 2Hm).
2
2
0.77 (m, 4H, meso), 7.04 (s, 2Ho (OPh)), 6.95 (s, 2Hm
For C H N OClRe anal. calcd. (%): C, 62.51; H,
48
52
4
OPh)), 6.85 (s, 1H (OPh)).
p
5.64; N, 6.08.
1
1
H– H 2D COSY NMR (C D ),
δ, ppm: 4.43 (m,
Found (%): C, 61.05, H, 5.45, N, 5.41.
6
6
3
2H, CH )–1.83 (m, CH ), 4.03 (m, 16H, CH )–
2
3
2
The solid samples of the products were isolated
from solutions after chromatography by evaporation
1
.83 (m, CH3).
For C H N O Re anal. calcd. (%): C, 60.94, H, of the solvent at room temperature. The individual
42
49
4
2
5
.93, N, 6.77.
Found (%): C, 62.17; H, 6.31; N, 7.15.
2,3,7,8,12,13,17,18ꢀOctaethylporphinato)(oxo)(chloꢀ
nature and the purity of the compounds were conꢀ
firmed by TLC on Silufol silica gel using a 10 : 1
CH Cl –C H OH mixture for compounds 1 (Rf = 0.52),
2
2
2
5
(
2
(
Rf = 0.64), and
The UVꢀVis spectra were recorded on an Agilent
453 UVꢀVis spectrophotometer, the IR spectra were
3 (Rf = 0.50).
ro)rhenium(V) O=Re(Cl)OEP (2). The complex was
prepared from O=Re(OPh)OEP by passing HCl gas
for 10 min through a solution of O=Re(OPh)OEP in
CH Cl . During this period, the solution color
8
measured on a Vertex 80v spectrophotometer; and
2
2
1
H NMR spectra were run on a Bruker Avance IIIꢀ500
changed from greenꢀyellow to pink. The yield was
00%.
UVꢀVis (CH Cl ),
spectrometer. Elemental analysis was performed on
CHNSꢀO Analyzer Flash EA 1112 Series. The UVꢀVis
1
λmax, nm (log
ε
): 620 (3.90), 518 spectra were recorded as plots and tables for the subseꢀ
2
2
(
4.30), 347 (4.92).
quent mathematical processing.
–1
IR (KBr),
ν
, cm : pyrrole rings, 1468 (
(C–N)); alkyl kinetic experiments was monitored by spectrophoꢀ
(C–H)); methine groups, 1223, 1271 tometry. The measurements were carried out in 1ꢀcm
(C–H)), 846, 854, 871 ( (C–H)); coordination cenꢀ thick cells placed into a special chamber maintained in
ter, 965 (Re=O), 467 (Re–N).
ν
(C=N)),
The decrease in the substance concentrations in
1
376 ( (C–N)), 1057 (C –C ,
ν
ν
3
4
groups, 1316 (
δ
(δ
γ
a thermostat in the cell holder of the spectrophometer.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 59 No. 12 2014