Synthesis of phosphine-containing dipyrromethene cobalt complexes, promising ligands for homogeneous catalysis in nanomembrane reactors

Article abstract of DOI:10.1134/S1070428016110130

Complexes of 5-(4-diphenylphosphinophenyl)dipyrromethene with trivalent cobalt (Ph₂PC₆H₄DP)₃Co (DP for dipyrromethene) were obtained for the first time, and their reaction with dicarbonylrhodium(I) acetylacetona

Full text of DOI:10.1134/S1070428016110130

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2016, Vol. 52, No. 11, pp. 1625–1631. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © E.A. Leushina, D.N. Gorbunov, D.A. Cheshkov, T.S. Kuchinskaya, A.V. Anisimov, A.L. Maksimov, M.V. Terenina, A.V. Khoroshutin,
E.A. Karakhanov, 2016, published in Zhurnal Organicheskoi Khimii, 2016, Vol. 52, No. 11, pp. 1631–1637.
Synthesis of Phosphine-Containing Dipyrromethene Cobalt
Complexes, Promising Ligands for Homogeneous
1
Catalysis in Nanomembrane Reactors
a
a
b
a
E. A. Leushina , D. N. Gorbunov , D. A. Cheshkov , T. S. Kuchinskaya ,
a
a,c
a
A. V. Anisimov , A. L. Maksimov ,* M. V. Terenina ,
a
a
A. V. Khoroshutin ,* and E. A. Karakhanov
a
Lomonosov Moscow State University, Leninskie Gory 1, bldg 3, GSP-1, Moscow, 119991 Russia
e-mail: khorosh@petrol.chem.msu.ru, max@ips.ac.ru
*
b
State Research Institute of Chemistry and Technology of Organoelemental Compounds, Moscow, Russia
c
Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, Russia
Received May 23, 2016
Abstract—Complexes of 5-(4-diphenylphosphinophenyl)dipyrromethene with trivalent cobalt (Ph
2 6 4 3
PC H DP) Co
(
DP for dipyrromethene) were obtained for the first time, and their reaction with dicarbonylrhodium(I)
1
13
2 6 4 3
acetylacetonate was investigated. The formed complex [Ph P(Rh)C H DP] Co was characterized by H, С,
31
and P NMR spectroscopy. The dimensions of the ligand were estimated (by geometry optimization with PM3
method) and of the formed rhodium complex (by 2D diffusion NMR spectroscopy DOSY). The size of the
complex makes it possible to detain it on membranes with the pore size of 2 nm providing an opportunity to use
it in catalytic processes with subsequent separation of the catalyst and the reaction products in the nanofiltration
mode. Test of 1-octene hydroformylation with the use of this catalytic system showed results similar to those
3
with the system Rh–PPh both with respect to conversion in aldehydes and to the ratio of n/iso-products. Thus
the fundamental possibility was demonstrated of applying the synthesized complexes in catalysis.
DOI: 10.1134/S1070428016110130
In the course of several last decades the problem of
separation of the homogenous catalyst from the
reaction mixture while conserving its activity and the
possibility of its further application is the subject of
numerous both laboratory and engineering studies. As
the main approaches to the solution of this problem the
distillation of the reaction products with the solvent
was tried; application of various two-phase systems
where the catalyst was mostly in one phase, and the
reagents and products in another was tested [1]. A
large number of studies were also connected with
designing “clever” catalysts where the active site was
bound to a polymer capable of crystallizing from the
reaction mixture or dissolving in it at changes in the
temperature [2].
membrane with nanosized pores which detain the
catalyst and let pass the solvent with reagents and
reaction products in the mode of nanofiltration at
pressure. To this end the catalyst should have
dimensions exceeding the pores diameter. To reach
this goal the active sites may be applied on polymer
carriers [3–5] (in particular, dendrites [6]), and also
grafted on nano particles [7].
The target of this study was the synthesis of a
ligand for subsequent coordination to Rh(I), a
catalyst of hydroformylation, in order to obtain a
complex of sufficiently large size to be detained
by a nanoporous membrane, and the estimation
of the size of this complex and its applicability
as a catalyst of alkenes hydroformylation. To reach
the chosen goals a synthesis was carried out of
a compound containing coordination centers of
two types: for binding to a metal not involved in
the catalysis of the reaction (in order to attain the
One of promising solutions of the problem is
applying reactors with a “window” made of a
1
Supplementary material is available at http://link.springer.com/.
1
625

1
626
LEUSHINA et al.
required dimensions), and for binding Rh(I) (to form
the catalytic centers).
The preliminary calculations of the geometry of
complex 5 by PM3 method show that the distance
between phosphorus atoms is ~1.7 nm, and the most
removed protons of the phenyl groups (meta-H in PPh2
groups) are apart from each other by 2.2 nm. Taking
into account that the phosphine groups of these
complexes will be present in the coordination sphere of
one more metal (e.g., rhodium), the overall size of this
catalyst should considerably exceed 2 nm. Therefore
We chose as the basis of the ligand dipyr-
romethenes 1. The dipyrromethenes being mono anion
8
10
bidentate ligands are known to form with d –d metals
N
N
N
N
N
N
N
N
M
N
PPh2
M
NH
N
N
PPh
2
1
2
3
N
N
N
strong complexes of 2 : 1 composition 2 (of elongated
tetrahedron structure) and of 3 : 1 composition 3
N
Co
N
(
octahedral) [8].
NH
N
N
By introducing in the composition of dipyr-
PPh
2
romethene of additional coordinating phosphine
substituents, for instance, 4-diphenylphosphinophenyl,
these complexes would become suitable for further
modification with metal ions capable of catalyzing,
e.g., cross-coupling reactions (Pd, Ni, etc.) or hydro-
formylation (Rh). We chose as the target dipyrro-
methene 5-[4-(diphenylphosphino)phenyl]dipyrrome-
thene 4, and as the model complex, catalyst precursor,
tris(dipyrrinato)cobalt 5. The preference between the
tetra- and octacoordinated complexes is for the latter
since the attack of nucleophiles on the octahedral
complexes that may destroy it is sterically hindered.
2
Ph P
4
5
the calculations confirm that compound 5 is a
promising precursor for the formation of homogeneous
catalyst capable of being detained on a membrane with
an average pore size 2 nm.
The synthesis of compound 4 was carried out by
procedure [9] through the corresponding dipyrro-
methane. p-Diphenylphosphinobenzaldehyde 6 [10]
was converted in the corresponding dipyrromethane 7
Scheme 1.
P
P
O
O
N
N
H
DDQ
m-Ar
o-Ar
g
TFA, 3 h
CH
2
Cl
2
,
meso-
2
Ph P
6 h
7
3
b
8
2
NH HN
NH
a
9
1
6
7
8
P(O)Ph
2
O
N
H
DDQ
TFA, 3 h
CH
2
Cl
2
,
2
Ph (O)P
6 h
NH HN
9
10
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 11 2016

SYNTHESIS OF PHOSPHINE-CONTAINING DIPYRROMETHENE COBALT COMPLEXES
1627
Scheme 2.
P(O)Ph2
Ph (O)P
2
Na [Co(NO ) ],
3
2 6
(
C H ) N
2 5 3
8
N
N
N
+
N
Co
CHCl3_CH OH H O
_
3
2
N
N
Co
N
2
N
P(O)Ph
2
Ph (O)P
2
11
12
that was oxidized with 2,3-dichloro-5,6-dicyanoqui-
none (DDQ). Yet instead of the expected compound 4
we obtained exclusively phosphine oxide 8. In the
reaction of substance 7 with a deficit of DDQ we have
found that phosphorus atom is the first to be oxidized
and only afterwards the dipyrromethane. 5-[4-(Diphenyl-
phosphoryl)phenyl]dipyrromethene 8 can also be ob-
tained from the corresponding aldehyde 9 (Scheme 1).
substituent in the dipyrromethene.
A
strong
dependence of the compound yield on the substituent
nature was as well observed before. For instance, it
was shown in [14, 15] that at the application the same
procedure to complexes preparation from 5-(4-
cyanophenyl)dipyrromethene and 5-(4-pyridylphenyl)-
dipyrromethene the yields of the products were 67 and
38% respectively.
Therefore the impossibility to prepare the
The reduction of compound 11 by procedure [16]
with trichlorosilane and triethylamine in toluene
afforded the desired compound 5.
dipyrromethene containing a Ph P group by the known
2
methods requires the reduction of the phosphoryl
group into phosphine one after its formation.
The structure of obtained new compounds 7–13
We tried to reduce compound 8 by the system
trichlorosilane–triethylamine. The reaction provided a
complex mixture of products, the characteristic color
of dipyrromethene disappeared, and in the composition
1
31
13
was confirmed by Н, P, and C NMR spectra. For
instance, in the spectra of compounds 7 and 8 the
chemical shifts of the dipyrromethane fragment are
materially the same, the signals of the aromatic
fragments bound to phosphorus are in agreement with
1
of the reaction mixture by H NMR spectroscopy
signals were detected (~5.2 ppm), corresponding to
dipyrromethanes. Apparently the conjugated system of
the dipyrromethene is unstable under stringent
reductive conditions used in the process.
1
the published data [17, 18]. In the H NMR spectrum
1,9
of compound 8 the doublet of protons H appears
at 7.65 ppm, and in the spectrum of compound 11
it is shifted upfield by 1.28 ppm due to the occurrence
1
,9
of the protons H in the field of the anisotropic
influence of another dipyrromethene ligand in the
octahedral complex 11. Similar effect was previously
observed in the octahedral dipyrromethene complexes
of Ru [19].
Therefore we decided first to prepare the complex
3
+
of Сo with compound 8 and to attempt to reduce the
phosphoryl group in the complex. The reaction of
compound 8 with Na [Co(NO ) ] [11] by procedure
3
2 6
[
12] furnished tris(dipyrrinato)cobalt 11 (Scheme 2).
In the course of the reaction the formation was
also observed of a dark-red substance whose mass
spectrum indicated the formation of a complex 12
The hydroformylation catalysts we obtained in situ
by the reaction of the ligand with the solution of
dicarbonylrhodium(I) acetylacetonate. The formation
of the catalytic complex was confirmed by the
disappearance of the signal at –5.64 ppm (the study of
the formation of the catalytic complex for
[
(
[
Ph P(O)C H DP] Co. Its electron absorption spectrum
2 6 4 2
EAS) is also well consistent with the published data
13]. The rather low yield of compound 11, obtained in
our experiment may be due to the nature of the aryl
hydroformylation was performed in a mixture CDCl –
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 11 2016

1
628
LEUSHINA et al.
Scheme 3.
[
Rh(I)], CO, H2
C H
8
+
C H
8
+ i-C H17CHO
+
C H17CHO
8
18
16
8
Mixture of
isomers
Mixture of
isomers
CD OD, 1 : 1) and the appearance of a characteristic
Since in our study the self-diffusion coefficients of
the two substances are nearly identical we assume also
the close values of their hydrodynamic radii. Conse-
3
3
1
doublet at 30.7 ppm in the P NMR spectrum with the
1
spin-spin coupling constant 153 Hz. In the Н NMR
spectrum the signals of phenyl groups shifted
downfield.
quently, the diameter of the complex [Rh(CO) ]·5 is
3
about 1.8 nm. Therefore the hydroformylation catalyst
based on the ligand 5 would apparently be detained by
the ultrathin membranes with pores of 2 nm.
The hydrodynamic radius of the formed rhodium
complex was estimated through the self-diffusion
coefficient D measured in DMSO-d by the method
6
We performed a test experiment of hydro-
formylation of 1-octene in the presence of complex
–
6
2
2
D-DOSY: log D–9.87, D 1.3×10 cm /s. For the
sake of comparison, the self-diffusion coefficient
was measured in identical conditions for PEG 1000
[
Rh(CO) ]·5 obtained in situ and compared it with the
3
results of runs carried out in identical conditions
–6
2
(
log D–9.84, D 1.44×10 cm /s), whose hydrodynamic
(
Scheme 3).
radius had been previously measured in methanol
by viscometry (ca. 0.92 nm) [20]. The self-diffusion
The results are collected in the table. These data permit
a conclusion that the complex [Rh(CO) ]·5 is no worse in
coefficient of PEG 1000 in methanol-d under
3
4
–
6
2
conversion and selectivity to the products of normal
structure than either the free Rh(I) ions or the rhodium
complexes with triphenylphosphine (runs 1, 2, 3). On the
other hand, we failed to compare the catalyst selectivity
the same conditions (log D–9.24, D 5.72×10 cm /s)
is in agreement with the coefficient in DMSO-d6
according to Stokes–Einstein equation within 15%
accuracy.
Comparison of 1-octene hydroformylation under catalysis by rhodium complex obtained in situ from various phosphine
ligands.
Ligand concn.,
mmol/L
(phosphorus mass
Content in the mixture of reaction
products, %
Ratio of
products of n-
and iso-
Mass of
ligand,
Run
no.
Ligand
(ratio P/Rh)
Catalyst
mg (µmol) fraction in reaction
mixture, ppm)
octene octane iso-octenes aldehydes structure
Rh(acac)(CO)
2
0
.5 mg (in 0.5 mL
of toluene),
с(Rh)=1.06mmol/L
а
without
ligand
1
–
–
2
4
7
89
0.6
а
2
PPh
3
(5 : 1) 2.5 (9.5)
3.8 (3.1)
5.3 (200)
1.7 (200)
4
2
1
1
9
8
6
1
7
10
10
5
80
80
83
93
1
0.8
2
а
3
5 (5 : 1)
а
4
PPh
PPh
3
3
(20 : 1) 10 (38)
(40 : 1) 20 (76)
21.1 (800)
42.2 (1000)
а
5
2
Rh(acac)(CO)
.5 mg (in 0.5 mL
of toluene),
с(Rh)=1.46mmol/L
2
0
b
6
PPh
3
(20 : 1) 10 (38)
29.2 (1000)
1
4
–
8
–
87
–
2.2
–
b
7
5 (20 : 1)
100
а
Reagents and conditions: 0.3 mL (1.9 mmol) of 1-octene, 1 mL of toluene, 80°С, 3 h, synthesis gas pressure 30 at, solution volume
.8 mL, solution mass 1.5 g; 0.3 mL (1.9 mmol) of 1-octene, 0.5 mL of toluene, 80°С, 3 h, synthesis gas pressure 30 at, solution
b
1
volume 1.3 mL, solution mass 1.1 g.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 11 2016

SYNTHESIS OF PHOSPHINE-CONTAINING DIPYRROMETHENE COBALT COMPLEXES
1629
1
with respect to the product of the normal structure under
conditions of the large excess of phosphine of a low
molecular weight since excess of compound 5 with respect
to rhodium led to the formation of a complex insoluble in
water which did not catalyze the reaction (run 7).
H NMR spectrum 2D-DOSY was registered on a
spectrometer Bruker Avance 600 applying a standard
pulse sequence ledbpgp2s [23] with stimulated spin
echo, gradient pulses of the magnetic field of sin form
and longitudinal eddy current delay. The current of the
gradient inductor changed linearly, stepwise from 2 to
95% from the maximum (10А), in 64 steps. The
maximum value of the gradient of the magnetic field
(at 10А current) was 53.5 G/cm. Time delay for
diffusion 40 ms, the length of gradient pulses 2 ms.
Relaxation delay 1 s. The obtained array of diffusion
data was processed using software XWinNMR 3.5
[24]. The Stokes–Einstein equation connecting the
diffusion coefficient (D), solvent viscosity (h),
temperture (T), and the particle size (r):
Thus in this study we have established for the first
time that complex compounds of the dipyrromethenes
series having on the periphery phosphine ligands may
serve as a platform for the formation of rhodium
hydroformylation complexes that due to their
dimensions may be detained by the membranes with
pore size 2 nm.
EXPERIMENTAL
k T
B
,
In the study initial reagents and solvents were used
purchased from Reakhim, Aldrich, Acros Organic.
D =
6
πηr
where k is Boltzmann’s constant.
Rh(acac)(CO) was synthesized by procedure [21]. All
B
2
1
solvents were distilled by standard methods [22]. Н,
С, and Р NMR spectra were registered on a
The calculation of the geometry of complex 5 and
oscillations calculation was carried out by PM3
method implemented in the program Hyperchem 7.01
for Windows.
1
3
31
spectrometer Bruker Avance 400. Chemical shifts of
the signals corresponding to quaternary and secondary
1
3
carbon atoms in the С NMR spectra registered in
ATP (attached proton test) regime are marked with an
asterisk. Mass spectra with the laser desorption
ionization (LDI-TOF) were recorded on an instrument
Bruker Daltonics Autoflex II at the irradiation with the
nitrogen laser at the wavelength 337 nm and
accelerating voltage 19 kV. The theoretic calculation
of the distribution of isotope peaks was carried out
using the program IsotopeViewer Version 1.0.
Electron absorption spectra were recorded on a
spectrophotometer Agilent-8453, operating range 190–
4
-(Diphenylphosphino)benzaldehyde (6) was syn-
thesized by procedure [10] in three stages from p-
bromobenzaldehyde. White crystals, mp 65–68°С. Н
NMR spectrum (CDCl ), δ, ppm: 7.31–7.42 m (12H,
Ph, m-Ar), 7.80 dd (2H, o-Ar, J 1.4, 8.3 Hz), 9.99 s
1
3
31
(
1H, CHO). P NMR spectrum (CDCl ), δ, ppm: –4.17.
3
4-(Diphenylphosphoryl)benzaldehyde (9) was
isolated as a side product in the synthesis of compound
as white crystals, mp 282°С. Н NMR spectrum
CDCl ), δ, ppm: 7.46–7.51 m (4H, m-Ph), 7.56–7.60
m (2H, p-Ph), 7.65 d.d (4Н, o-Ph, J 7.0, JP-H 12.2 Hz),
.85 d.d (2Н, J 8.2, JP-H 11.4 Hz, m-Ar), 7.95 d.d (2Н,
J 8.4, JP-H 2.6 Hz, o-Ar), 10.08 s (1H, CHO). P NMR
spectrum (CDCl ), δ, ppm: 28.84.
1
6
(
3
1
100 nm. The spectrophotometer control, data
7
collection and the simplest mathematical processing of
data was performed with the help of the program UV-
Visible Chem. Station Rev. A. 10.01, as well as on the
instrument Flyuorat-02-Panorama. Fluorescence spectra
were registered on a spectrofluorimeter Flyuorat-02-
Panorama. TLC was done on DC-Alufolien Kieselgel
3
1
3
5
-[4-(Diphenylphosphino)phenyl]dipyrrometha-
ne (7) was prepared by procedure [9]. 2 mL (1.86 g,
7.8 mmol) of pyrrole was stirred in an argon flow for
2
6
0 F2 (Merck) plates. The column chromatography
54
10 min. Then 0.27 g (0.93 mmol) of 4-(diphenylpho-
sphino)benzaldehyde 6 [10] was added, and the
reaction mixture was stirred in an argon flow for
another 10 min. Trifluoroacetic acid (7 µL, 0.09 mmol)
was added, the reaction mixture was stirred for 3 h.
After adding several granules of NаOH the alkali was
filtered off, excess pyrrole was removed from the
reaction mixture by distillation in a vacuum of an oil
pump (~0.1 mmHg). The obtained brown-orange oily
was performed with the use of silica gel Merck, pores
diameter 60 Ǻ, particle size 0.063–0.200 mm. Analysis
of the hydroformylation products was performed by
GLC using internal reference (nonane) on
a
chromatograph Hewlett-Packard equipped with flame-
ionization detector. Capillary column HP-1 (50000 ×
0
.32 mm, stationary phase cross-linked methyl-
siloxane, 0.52 µm), ramp 60–230°С.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 11 2016

1
630
LEUSHINA et al.
substance was dissolved in CH Cl and passed through
dicyanobenzoquinone in 4 mL of СH Cl . The reaction
2
2
2
2
a silica gel bed, the solution was evaporated to dryness
mixture was stirred at room temperature for 6 h, then it
was evaporated to dryness. The obtained dark
substance was dissolved in a mixture chloroform + 3%
of methanol and passed through a filter with silica
gel. Yield 169.9 mg (0.086 mmol, 65%), brown
substance.
on a rotary evaporator. Yield 0.254 g (0.62 mmol,
1
6
7%), light-yellow oily substance. Н NMR spectrum
(
DMSO-d ), δ, ppm: 5.35 br.s (1Н, meso-Н), 5.65–
6
5
.67 m (2Н, γ-Н), 5.87–5.89 m (2Н, β-Н), 6.59–6.60
m (2Н, α-Н), 7.14–7.25 m (8H, o-Ph, m-Ar), 7.35–7.39
1
3
m (6H, m,p-Ph), 10.57 br.s (2H, NH). С NMR
b. Compound 8 was obtained from 289.7 mg
(0.686 mmol) of compound 10 and 172 mg (0.755 mmol)
spectrum (DMSO-d ), δ, ppm: 43.25 (meso-С), 106.18,
6
3
3
1
6
06.93, 116.93, 128.53 d ( J 7.0 Hz), 128.71 d ( J
.6 Hz), 128.86, 131.44 d ( JP-C 9.6 Hz), 133.14 d ( JP
9.2 Hz), 132.68, 133.27 d ( J 19.2 Hz), 133.89 d
JP-C 10.3 Hz), 136.93 d ( J 11.1 Hz), 144.91.
P-C P-C
1
1
2
of DDQ. Yield 64.3 mg (0.153 mmol, 61%). Н NMR
3,7
2
spectrum (CDCl ), δ, ppm: 6.39 d.d (2Н, H , J 1.2,
3
1
-
C
P-C
2,8
1
1
31
4.2 Hz), 6.53 d (2Н, H , J 4.1 Hz), 7.48–7.52 m (4Н,
o-Ph or Ar), 7.55–7.59 m (4Н, o-Ph or Ar), 7.64–7.66
m (2Н, H ) 7.70-7.74 m (6H, m,p-Ph). С NMR spec-
trum (CDCl ), δ, ppm: 117.95, 128.61 d ( J 12.2 Hz),
12.2 Hz), 131.32 d ( J
10.0 Hz), 132.04 d ( J 104.7 Hz), 132.04 d ( J
(
Р
P-C
NMR spectrum (DMSO-d ), δ, ppm: –7.34.
6
1,9
13
3
5
-[4-(Diphenylphosphoryl)phenyl]dipyrrome-
thane (10) was synthesized from 2 mL (1.86 g,
7.8 mmol) of pyrrole by procedure [9]. In an argon
3
P-C
3
2
128.76, 130.72 d ( J
P-C
P-C
1
2
2
P-C
P-C
1
flow 0.37 g (1.2 mmol) of 4-(diphenylphosphoryl)ben-
zaldehyde 9 was added, the mixture was stirred for 10 min,
then 9 µL (0.12 mmol) of trifluoroacetic acid was added,
the reaction mixture was stirred for 1 h. After adding
several granules of NаOH the mixture was stirred for
10.4 Hz), 132.14, 133.42 d ( J 102.9 Hz), 140.17,
P-C
31
140.40, 140.86, 144.12. Р NMR spectrum (CDCl3),
δ, ppm: 30.00. EAS (CH CN), λ , nm: 427 (e
427
3
max
4
+
.
7.6×10 ) Mass spectrum: m/z 421 [M + H] Isotope
.
distribution of peaks is consistent with calculations.
2
0 min, the alkali was filtered off, excess pyrrole was
Complex formation of 5-[4-(diphenylphospho-
ryl)phenyl]dipyrromethene 8 with Сo(III) [14]. To a
solution of 35.1 mg (0.084mmol) of compound 8 in 15 mL
of a mixture chloroform–methanol, (1 : 1), under inert
atmosphere was added 0.2 mL of triethylamine and a
solution of 10.6 mg (0.028 mmol) of Na [Co(NO ) ]
[11] in 3 mL of a mixture methanol–water, 1 : 1. The
reaction mixture was stirred for 24 h at room
temperature, then it was washed with water, the
organic phase was separated and evaporated. The
obtained precipitate was dissolved in chloroform, at
adding to the solution petroleum ether dark-red bis-di-
pyrrinate complex precipitated, tris-dipyrrinate Сo(III)
remained in solution.
removed from the reaction mixture by distillation in a
vacuum of an oil pump (~0.1 mmHg). The obtained
dark oily substance was dissolved in ethyl acetate. The
reaction product was isolated by column chromato-
graphy on silica gel (eluent ethyl acetate + 6% of
3
2 6
ethanol + 1% of triethylamine). Yield 0.32 g (0.75 mmol,
6
1
3%) light-yellow oily substance. Н NMR spectrum
(
DMSO-d ), δ, ppm: 5.41 br.s (1Н, meso-Н), 5.66–
6
5
.68 m (2Н, γ-Н), 5.88–5.90 m (2Н, β-Н), 6.59–6.61
m (2Н, α-Н), 7.31 d.d (2Н, J 2.5, 8.2 Hz, o-Ar), 7.49–
7
1
3
.62 m (12H, Ph, m-Ar), 10.58 br.s (2H, NH).
С
(
DMSO-d ), δ, ppm: 43.36 (meso-СН), 106.28, 106.97,
6
3
3
1
1
9
1
17.06, 128.38 d ( J
12.2 Hz), 128.68 d ( J
P-C
P-C
1
2
1.8 Hz), 130.19 d ( J 103.9 Hz), 131.40 d ( J
.8 Hz), 131.42 d ( J 10.2 Hz), 131.91 d ( J 2.6 Hz),
P-C
P-C
2
4
P-C
P-C
Tris{5-[4-(diphenylphosphoryl)phenyl]dipyrri-
1
4
32.22, 132.93 d ( J 102.5 Hz), 147.98 d ( J 2.8 Hz).
P-C
P-C
nato}cobalt(III) (11) Yield 37.5 mg (0.0285 mmol,
3
1
Р NMR spectrum (DMSO-d ), δ, ppm: 26.38.
1
6
3
(
4%). Н NMR spectrum (CDCl ), δ, ppm: 6.31 d.d
3
3
,7
1,9
2Н, H , J 1.6, 4.4 Hz), 6.36–6.40 m (2Н, Н ), 6.65
5
-[4-(Diphenylphosphoryl)phenyl]dipyrromethe-
2
,8
d.d (2Н, H , J 1.3, 4.3 Hz), 7.47–7.60 m (8H, Ar, o-
PhH), 7.69–7.75 m (6H, m,p-Ph). Р NMR spectrum
ne (8) was synthesized from 5-[4-(diphenylphosphi-
no)]phenyldipyrromethane 7 and from 5-[4-(diphenyl-
phosphoryl)]phenyldipyrromethane 10 under known
conditions [25].
31
(
CDCl ), δ, ppm: 29.33. EAS (CH Сl ), λmax, nm:
3
2
2
4
4
4
1
1
70 (ε470 2.6×10 ), 505 (ε
= 2.3×10 ). Found M
505
317.3309. C H СoN O Р . Calculated
M
8
1
60
6
3
3
a. A solution of 150 mg (0.37 mmol) of compound
317.3345.
Tris{5-[4-(diphenylphosphino)phenyl]dipyrrina-
to}cobalt(III) (13) was synthesized from compound
7
in 10 mL of СH Cl was flushed with argon, cooled
2 2
in ice bath, then added dropwise to a flask containing a
solution of 311.7 mg (1.364 mmol) of dichloro-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 11 2016

SYNTHESIS OF PHOSPHINE-CONTAINING DIPYRROMETHENE COBALT COMPLEXES
1631
1
1 by procedure [16]. To a solution of 1 g (7.52 mmol)
3. Bortenschlager, M., Schollhorn, N., Wittmann, A.,
and Weberskirch, R., Chem. Eur. J., 2007, vol. 13,
p. 520.
of trichlorosilane in 25 mL of anhydrous toluene was
added a solution of 33 mg (0.025 mmol) of compound
1
atmosphere to the reaction mixture 1 mL of
trimethylamine was added, the mixture was boiled for
6
volume, at stirring 5 mL of saturated NaHCO solution
was added. The obtained emulsion was passed through
a filter with silica gel. First orange fraction was
washed out with toluene. Yield 15.3 mg (0.012 mmol,
4
4
5
.
.
Jiang, M., Ding, Y., Yan, L., Song, X., and Lin, R.,
Chin. J. Catal., 2014, vol. 35, p. 1456.
Jiang, M., Yan, L., Sun, X., Lin, R., Song, X., Jiang, Z.,
and Ding, Y., Reaction Kinetics Mechanisms Catal.,
1 in 5 mL of toluene. At stirring under inert
h, then the solution was evaporated to 1/3 of the
2
015, vol. 116, p. 223.
3
6. Ricken, S., Osinski, P.W., Eilbracht, P., and Haag, R.,
J. Mol. Catal. A: Chem., 2006, vol. 257, p. 78.
7. Garcia, M.A.S., Oliveira, K.C.B., Costa, J.C.S., Corio, P.,
Gusevskaya, E.V., dos Santos, E.N., and Rossi, L.M.,
ChemCatChem., 2015, vol. 7, p. 1566.
1
8%). Н NMR spectrum (CDCl ), δ, ppm: 6.31 d.d
3
3
,7
1,9
8
.
Wood, T.E. and Thompson, A., Chem. Rev., 2007,
(
2Н, H , J 1.7, 4.2 Hz), 6.40–6.41 m (2Н, Н ), 6.73
2
,8
vol. 107, p. 1831.
d.d (2Н, H , J 1.3, 4.3 Hz), 7.32–7.39 m (12H, ArH,
Ph), 7.22 d.d (2H, J 1.5, 8.3 Hz). С NMR spectrum
1
3
9. Littler, B.J., Miller, M.A., Hung, C.-H., Wagner, R.W.,
O'Shea, D.F., Boyle, P.D., and Lindsey, J.S., J. Org.
Chem., 1999, vol. 64, p. 1391.
3
(
CDCl ), δ, ppm: 118.69, 128.61 d ( J 7.2 Hz), 128.92,
3 P-C
3
2
130.53 d ( J
6.8 Hz), 132.35 d ( J
19.2 Hz),
P-C
P-C
1
0. Hon, Y.-S., Lee, C.-F., Chen, R.-J., and Szu, P.-H.,
2
132.92, 133.81 d.d (J 1.2, J 19.8 Hz), 135.48, 136.79
P-C
Tetrahedron, 2001, vol. 57, p. 5991.
1
1
d.d (J 2.2, J 10.7 Hz), 137.92 d ( J 12.0 Hz)
1
δ, ppm: –4.46. EAS (CH Сl ), λmax, nm: 470 (ε470
2
11. Glemser, O. and Schwarzmann, E., Rukovodstvo po
neorganicheskomu sintezu (Guide for Inorganic
Synthesis), Brauer, G., Ed., Moscow: Mir, 1985, vol. 5.
P-C
P-C
31
38.29, 145.66, 151.81. Р NMR spectrum (CDCl3),
2
2
4
4
1
2. Halper, S.R., Stork, J.R., and Cohen, S.M., Dalton
Trans., 2007, p. 1067.
.3×10 ), 505 (ε
2.1×10 ). Found M 1269.3470.
05
5
C H СoN Р . Calculated M 1269.3497.
8
1
60
6 3
1
3. Fergusson, J.E. and Ramsay, C.A., J. Chem. Soc., 1965,
p. 5222.
Hydroformylation of 1-octene. The reaction was
carried out in a steel pressure reactor of 25 mL
capacity equipped with a magnetic stirrer and device
for temperature control. In the reactor was charged
14. Murphy, D.L., Malachowski, M.R., Campana, C.F., and
Cohen, S.M., Chem. Commun., 2005, p. 5506.
1
1
1
1
1
5. Halper, S.R. and Cohen, S.M., Inorg. Chem., 2005, vol. 44,
p. 486.
6. Friesen, C.M., Montgomery, C.D., Temple, S.A.J.U.,
J. Fluorine Chem., 2012, vol. 144, p. 24.
7. Solomon, S.A., Allen, L.K., Dane, S.B.J., and Wright, D.S.,
Eur. J. Inorg. Chem., 2014, vol. 2014, p. 1615.
8. Russell, M.G. and Warren ,S., J. Chem. Soc., Perkin
Trans. 1, 2000, p. 505.
9. Li, G., Ray, L., Glass, E.N., Kovnir, K., Khoroshutin, A.,
Gorelsky, S.I., and Shatruk, M., Inorg. Chem., 2012,
vol. 51, p. 1614.
Rh(acac)(CO) , 1-octene, nonane (reference for GLC
2
analysis), and a calculated mass of a phosphine ligand
(see the table). The reactor was twice flushed with
argon and filled with synthesis gas (CO-H , 1 : 1) to
2
the desired pressure, and the reaction was performed
within the indicated time. The reactor was cooled, the
pressure was carefully removed, products were
analyzed by GLC.
The study was carried out under the financial
support of the Ministry of Education and Science of
the Russian Federation (Federal targeted program
2
0. Dohmen, M.P.J., Pereira, A.M., Timmer, J.M.K.,
Benes, N.E., and Keurentjes, J.T.F., J. Chem. Eng.
Data, 2008, vol. 53, p. 63.
“
Investigations and developments in priority directions
2
2
1. Varshavskii, Yu. and Cherkasova, T.G., Zh. Neorg.
Khim., 1967, vol. 12, p. 1709.
of the advancement of the R&D complex of
Russia for 2014–2020,” event 1.3, grant assignment
no. 14.607.21.0083). Unique identifier of applied
scientific studies (project) RFMEFI60714X0083.
2. Organikum. Organisch-chemisches Grundpraktikum,
Wienheim: Wiley, 2004, 22nd edn. Translated under the
title Organikum, Moscow: Mir, 2008, vol. 2.
3. Wu, D.H., Chen, A.D., and Johnson, C.S., J. Magn.
Reson., Ser. A, 1995, vol. 115, p. 260.
2
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 11 2016