Gallium Complexes with Acenaphthene-1-Imino-2-one: Synthesis and Reactivity

Article abstract of DOI:10.1134/S1070328418060040

The reduction of acenaphthene-1-(2,6-diisopropylphenyl)imino-2-one (Dpp-Mian) by gallium in the presence of iodine primarily results in a bis(ligand) paramagnetic derivative [(Dpp-Mian)₂GaI] and then to a dimeric diamagnetic complex [(Dpp-Mian)

Full text of DOI:10.1134/S1070328418060040

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2018, Vol. 44, No. 6, pp. 380–387. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © D.A. Razborov, A.N. Lukoyanov, M.V. Moskalev, E.V. Baranov, I.L. Fedyushkin, 2018, published in Koordinatsionnaya Khimiya, 2018, Vol. 44,
No. 3, pp. 176–183.
Gallium Complexes with Acenaphthene-1-Imino-2-one:
Synthesis and Reactivity
D. A. Razborova, A. N. Lukoyanova, M. V. Moskaleva, E. V. Baranova, and I. L. Fedyushkina, *
aRazuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhny Novgorod, 603600 Russia
*е-mail: igorfed@iomc.ras.ru
Received September 7, 2017
Abstract—The reduction of acenaphthene-1-(2,6-diisopropylphenyl)imino-2-one (Dpp-Mian) by gallium
in the presence of iodine primarily results in a bis(ligand) paramagnetic derivative [(Dpp-Mian)2GaI] and
then to a dimeric diamagnetic complex [(Dpp-Mian)GaI]2, the reaction of which with PhC≡CH gives a cyc-
loaddition product [{Dpp-Mian(HC=CPh)}GaI]2. The new compounds are characterized by IR spectros-
copy and 1H NMR spectroscopy. The structures of complexes (Dpp-Mian)2GaI and [{Dpp-
Mian(HC=CPh)}GaI]2 are determined by X-ray structure analysis (CIF files CCDC nos. 1571860 and
1571861, respectively). The catalytic activity tests for compounds [(Dpp-Mian)GaI]2 and [{Dpp-
Mian(HC=CPh)}GaI]2 are conducted in the reactions of 4-chloroaniline with phenylacetylene and carbo-
diimide and in the reaction of phenylacetylene with 1-naphthol.
Keywords: gallium, N,O-ligands, synthesis, structure, X-ray structure analysis, hydroamination and hydro-
arylation of unsaturated substrates
DOI: 10.1134/S1070328418060040
INTRODUCTION
An interesting feature of these reactions is sub-
strate binding not only with the metal center but
also with the ligand due to carbon–carbon bond
formation. Similar processes were also observed for
the reactions of aromatic ketones with the zirco-
nium [2] and samarium [3] complexes containing
dianions of 1,4-diaza-1,3-dienes. Cycloaddition for
the nontransition metal complex (Dpp-Bian)Ga–
Ga(Dpp-Bian) (I) (Dpp-Bian is 2,6-(diisopropyl-
phenylimino)acenaphthene) has first been discov-
ered in 2010. Compound I reacts with diverse
alkynes to form stable cycloadducts [4, 5].
The cycloaddition of unsaturated substrates to
transition metal complexes with the neutral 1,4-diaza-
1,3-diene or 1,4-dihetero-1,3-diene ligand was des-
cribed [1]. For example, the iron and ruthenium com-
plexes with ketoimine ligands react with activated
alkynes to form stable cycloadducts.
E
E'
R3
R2
O
L
L
L
M L
L
R3
R2
O
E
E'
L
M
N
R1
N
R1
M = Fe, Ru; E = H, CO2Me;
E' = CO2Me; L = CO; PR3; Dppe
R
R'
Ar
N
Ar
N
Ar
N
Ga Ga
Ar
N
+R
R'
R'
Ga Ga
−R
N
N
N
N
Ar
Ar
Ar
Ar
R'
R
(I)
Ar = 2,6-diisopropylphenyl; R = H, R' = H; R = Ph; R' = H; R = CH , R' = C(O)OCH3
3
380

GALLIUM COMPLEXES WITH ACENAPHTHENE-1-IMINO-2-ONE
381
A unique specific feature of the cycloaddition of diimines seems promising. We have previously synthe-
alkynes to complex I is the complete reversibility of sized and characterized a series of the complexes with
the process, which phenomenologically resembles the neutral Dpp-Mian [18]. Magnesium amidoalkoxide
π-coordination of unsaturated organic molecules by [(Dpp-Mian)Mg(Тhf)2]2 (III) was synthesized by
transition metal compounds. Later these processes
were carried out on the aluminum compounds and
mononuclear gallium derivatives containing diimine
ligands. The reactivity of compounds of this class
toward alkynes depends on both the metal nature and
the type of the functionally labile ligand bound to the
metal. For example, dialane (Dpp-Bian)Al–Al(Dpp-
Bian) [6] and its 1,4-diaza-1,3-diene analog [7] are
more reactive in the reactions with alkynes than digal-
lane I. Complex (Dpp-Bian)Al–Al(Dpp-Bian) adds
methylphenylacetylene toward which digallane I is
inert. The mononuclear derivatives (Dpp-
Bian)AlEt(Et2O) and (Dpp-Bian)Ga(S2CNMe2) also
react with alkynes to form cycloadducts. In addition,
the latter can reversibly add methyl vinyl ketone [8, 9].
Unlike digallane I, the magnesium acenaphthene-
1,2-diimine complex (Dpp-Bian)Mg(Thf)3 (II) (Тhf
is tetrahydrofuran) in the reaction with phenylacety-
lene behaves as a frustrated Lewis pair [10–12] to give
the alkynylmagnesium derivative coordinating the
protonated amidoamine Dpp-Bian ligand [13].
reduction with magnesium [19]. Compound III is the
first acenaphthenequinoneimine derivative of the non-
transition metal and the first metal complex containing
the Dpp-Mian ligand in the reduced form. The reaction
of compound III with phenylacetylene illustrates
brightly the important role of redox-active ligands in
imparting these or other chemical properties to the
complexes with nontransition metals. Unlike related
compound II, complex III reacts with phenylacetylene
to give cycloadduct [(Dpp-Mian)(PhC=CH)Mg(Thf)]
(IV) similarly to digallane I. The reaction of cycload-
duct IV with the second equiv mol PhC≡CH affords the
phenylethynyl derivative [(Dpp-Mian)-(PhC=CH2)-
Mg(C≡CPh)(Thf)]2 (V).
Ar
N
+Ph
Toluene
O
80°C
Mg
(III)
Ar
O
O
Ph
C
O
(IV)
Ph
N
C
Mg
Thf
Ph
O
+Ph
−Thf
O
O
O
O
Ph
Ph
Thf
O
Mg
Mg
Mg
H
C
N
Ar
Ar
N
N
Ar
Ar
N
N
C
Ar
Ar = 2,6-diisopropylphenyl
Ph
(V)
+H
Ph
We attempted to synthesize new gallium complexes
with Dpp-Mian in order to extend concepts on the
properties of metal complexes with redox-active
ligands. In this work, we report the synthesis of the
gallium derivatives containing Dpp-Mian in various
redox states [(Dpp-Mian)2GaI] (VI), [(Dpp-Mian)-
GaI]2 (VII), and [{Dpp-Mian(HC=CPh)}GaI]2
(VIII) and the results of identification of the synthe-
(II)
Ar = 2,6-diisopropylphenyl
The ability of complex I to “coordinate” pheny-
lacetylene makes it possible to carry out the hydroam-
ination and hydroarylation of this alkyne by anilines
and 1-naphthol, respectively, in the presence of cata-
lytic amounts of compound I [5, 14]. In addition,
complex I catalyzes the addition of anilines to carbo-
diimides [15]. In turn, magnesium derivative II is an
efficient catalyst of the polymerization of lactides with
ring opening [16] and of the hydroamination of some
olefins by pyrrolidine [17].
Monoiminoquinones represent a transition struc-
ture from o-quinones to α-diimines. The properties of
monoiminoquinones, primarily, the redox potentials
and steric volume, have an intermediate character,
which allows one to expect the formation of new types
of complexes containing one or two redox-active
ligands in the same or in different reduction states and
demonstrating new types of reactivity. From the view-
point of preparing complexes of the new class, the
1
sized compounds in a solution using H NMR spec-
troscopy, determination of their molecular structures
in the crystalline state by X-ray structure method, and
investigation of the catalytic properties of the com-
pounds obtained.
EXPERIMENTAL
All procedures with unstable compounds VI, VII,
and VIII were carried out in vacuo or in an inert nitro-
gen atmosphere using the Schlenk technique. Solvents
(involving deuterated solvents) were dried over sodium
benzophenone ketyl and were taken by condensation
in vacuo prior to use. Compound Dpp-Mian was
obtained by a described procedure [19]. IR spectra
were recorded on an FSM-1201 spectrometer, and
monoiminoacenaphthenone ligands capable of mul- 1H NMR spectra were measured on a Bruker DPX 200
tielectron reducing similarly to acenaphthene-1,2- spectrometer.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 44 No. 6 2018

382
RAZBOROV et al.
Synthesis of [(Dpp-Mian)2GaI] (VI). A solution of temperature as colorless crystals. The yield was 0.22 g
(57%), mp = 152°C (decomp.).
Dpp-Mian (0.34 g, 1.0 mmol) and iodine (0.06 g,
0.5 mmol) in diethyl ether (15 mL) was poured to a
metallic gallium excess (3.0 g). Then the mixture was
heated in a water bath for 1 h. The color of the solution
gradually changed from red-orange to green. The
obtained solution was decanted. Compound VI was
crystallized from diethyl ether as green crystals. The
yield was 0.38 g (80%), mp = 181°C.
For C70H70N2O3.5I2Ga2
Anal. calcd., %
Found, %
C, 60.46
C, 60.53
H, 5.22
H, 5.19
N, 2.01
N, 1.97
IR (ν, cm–1): 3089 w, 3058 m, 3022 m, 1970 w,
1952 w, 1942 m, 1911 w, 1893 w, 1875 w, 1821 w,
1808 w, 1651 s, 1620 m, 1589 m, 1565 m, 1483 m,
1438 m, 1429 w, 1417 m, 1365 m, 1350 m, 1324 m,
1313 m, 1288 w, 1264 m, 1256 m, 1223 w, 1212 w,
1190 s, 1182 s, 1164 m, 1141 m, 1106 m, 1068 s, 1035 m,
1011 w, 999 w, 977 w, 968 w, 932 s, 911 m, 865 m,
841 m, 830 s, 805 s, 782 s, 769 s, 761 m, 713 s, 702 m,
674 m, 630 m, 604 m, 599 m, 582 m, 576 m, 558 m,
530 m, 504 m, 497 w, 468 m, 459 w.
1H NMR (δ, ppm): 0.36 d (CH(CH3)2), 1.12 d
(CH(CH3)2), 1.25 dd (CH(CH3)2), 1.49–1.36 m
(Thf), 2.87 sept. (CH(CH3)2), 3.65–3.50 m (Thf),
3.75 sept. (CH(CH3)2), 6.06 d (PhC=CH(H)), 6.66–
6.40 m (arom.), 7.42–6.90 m (arom.).
For C52H56N2O3IGa
Anal. calcd., %
Found, %
C, 65.49
C, 65.56
H, 5.92
H, 5.88
N, 2.94
N, 2.91
IR (ν, cm–1): 1931 w, 1876 w, 1814 w, 1742 w,
1600 m, 1525 m, 1320 m, 1252 w, 1194 w, 1111 w,
1099 w, 1089 w, 1057 w, 1033 m, 972 w, 948 m, 939 m,
911 w, 899 w, 829 m, 818 m, 806 m, 776 m, 766 s,
683 m, 636 m, 590 m, 576 m, 540 w, 520 w, 493 w,
457 w.
Synthesis of [(Dpp-Mian)GaI]2 (VII). A solution of
Dpp-Mian (0.34 g, 1.0 mmol) and iodine (0.13 g,
1.0 mmol) in diethyl ether (15 mL) was poured to a
metallic gallium excess (3.0 g). On heating in a water
bath for 1.5 h, the color of the solution changed from
red-orange to green and then to violet. The obtained
solution was decanted. After the solvent was removed,
the residue was washed with hexane. The yield was
0.33 g (61%), mp = 173°C.
Hydroamination of phenylacetylene and dicyclohex-
ylcarbodiimide by 4-chloroaniline and hydroarylation of
phenylacetylene by 1-naphthol. Catalytic tests were
carried out using known procedures [5, 14, 15]. Phe-
nylacetylene was preliminarily purified by distillation,
dried over metallic sodium, and sampled by conden-
sation in vacuo. The substrates (0.5 mmol each) and
catalyst (4–8 mol %) were placed in a preliminarily
1
For C48H46N2O2I2Ga2
evacuated ampule for H NMR spectroscopy, and
deuterated benzene (0.5 mL) was added to each
ampule. After this, the ampule was sealed and the 1H
NMR spectrum of a mixture of the starting reactants
was detected at room temperature. Then the reaction
mixture was heated in an oil bath in a temperature
range of 90–130°С. The process and conversion of the
Anal. calcd., % C, 53.57
Found, % C, 53.62
H, 4.31
H, 4.28
N, 2.60
N, 2.56
IR (ν, cm–1): 1932 w, 1875 w, 1813 w, 1741 w,
1602 m, 1527 s, 1490 s, 1421 m, 1365 w, 1319 m,
1253 w, 1194 w, 1111 w, 1099 w, 1089 w, 1057 w,
1033 m, 972 w, 948 m, 939 m, 911 w, 899 w, 829 m,
820 m, 807 m, 777 m, 766 s, 683 m, 636 m, 590 m, 577
m, 539 w, 521 w, 494 w, 456 w.
1
reactants were monitored by H NMR spectroscopy.
The ratio between the starting reactants and reaction
products was calculated from the integral intensities of
the corresponding signals.
X-ray structure analyses of compounds VI and VIII
were carried out on a Bruker D8 Quest diffractometer
(МоКα radiation, ω scan mode, λ = 0.71073 Å).
Experimental arrays of intensities were integrated
using the SAINT program [20]. Absorption correc-
tions were applied using the SADABS program [21].
The structures were determined by a direct method
(SHELXTL program package) [22–24] and refined by
1H NMR (δ, ppm): 0.24 d (CH(CH3)2), 1.04 d
(CH(CH3)2), 1.30 d (CH(CH3)2), 1.62 d (CH(CH3)2),
2.11 s (C6H5CH3), 2.86 sept. (CH(CH3)2), 4.17 sept.
(CH(CH3)2), 6.33 s (arom.), 6.58 d (arom.), 6.74 t
(arom.), 7.40–6.97 m (arom.).
Synthesis of [{Dpp-Mian(HC=CPh)}GaI]2 (VIII).
The heating of a mixture of compound VII (0.3 g,
0.28 mmol) and phenylacetylene (0.31 g, 3.0 mmol) in
Fh2kl
full-matrix least squares for
in the anisotropic
toluene (35 mL) at 90°С for 2 h resulted in a change in approximation for all non-hydrogen atoms. Hydrogen
the color of the reaction mixture from blue to violet. atoms were placed in the geometrically calculated
After the mixture was cooled down to room tempera- positions and refined by the riding model. The H(1)
ture, volatile components were removed in vacuo. The and H(2) atoms in complex VIII were found from the
remained solid was dissolved in Thf (15 mL) on heat- difference electron density synthesis and refined iso-
ing. Complex VIII was crystallized from Thf at room tropically. Solvate molecules of diethyl ether and Thf
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
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GALLIUM COMPLEXES WITH ACENAPHTHENE-1-IMINO-2-ONE
383
Table 1. Crystallographic data and the X-ray structure analysis parameters for compounds VI and VIII
Value
Parameter
VI
VIII
FW
953.60
100
1388.52
100
Т, K
Crystal system
Space group
a, Å
Monoclinic
P21/n
Triclinic
P1
13.7817(9)
13.1984(9)
24.456(2)
90
10.068(1)
16.111(2)
20.126(2)
103.553(2)
90.806(2)
93.539(2)
3166.2(6)
b, Å
c, Å
α, deg
β, deg
γ, deg
91.390(1)
90
V, Å3
4447.1(5)
Z
4
2
calc, g cm–3
1.424
1.456
ρ
μ, mm–1
1.358
1.874
F(000)
1960
0.70 × 0.63 × 0.51
2.28–28.00
–18 ≤ h ≤ 18,
–17 ≤ k ≤ 17,
–32 ≤ l ≤ 32
52331
1400
0.27 × 0.11 × 0.07
2.46–25.00
–11 ≤ h ≤ 11,
–19 ≤ k ≤ 19,
–23 ≤ l ≤ 23
28277
Crystal size, mm
Measurement range, θ, deg
Range of indices h, k, l
Number of observed reflections
Number of independent reflections
Rint
10726
10986
0.0295
0.0451
GOOF (F2)
1.013
1.041
R1/wR2 (I > 2σ(I))
R1/wR2 (for all parameters)
0.0264/0.0641
0.0329/0.0664
0.945/–0.469
0.0537/0.1462
0.0658/0.1539
2.979/–0.984
ρ
max/ρmin, e Å–3
were found in the general positions in crystals of com- 1571860 (VI) and 1571861 (VIII)) and are available at
www.ccdc.cam.ac.uk/structures/.
pounds VI and VIII, respectively. The ratios of the sol-
vate molecules to the gallium complex are 1 : 1 (VI)
and 1.5 : 1 (VIII). The diethyl ether molecule in com-
pound VI is disordered over two positions. Selected
crystallographic characteristics and the parameters of
X-ray structure experiments for compounds VI and
VIII are presented in Table 1.
RESULTS AND DISCUSSION
The reduction with a gallium excess in the presence
of an equivalent amount of iodine in Thf or diethyl
ether is accompanied by the subsequent change in the
color of the solution from red-orange to green and
then violet. This reaction gave two metal complexes VI
and VII formed consequently and containing ligands
The structures were deposited with the Cambridge
Crystallographic Data Centre (CIF files CCDC nos. in different reduction states.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 44 No. 6 2018

384
RAZBOROV et al.
Ar
N
Ar
N
+Ga(exc. )
+1/2I2
+Ga(exc. )
+1/2I2
I
Ga
O
I
Dpp-Mian
Ga
O
O
N
Ar
a
b
O
Ga
I
N
Ar
(VI)
(VII)
Ar = 2,6-diisopropylphenyl
The X-ray structure analysis of the crystals isolated and τ = 1 for a trigonal bipyramid. Later the synthesis
from a green solution shows that complex VI (Fig. 1)
containing two radical anion ligands is formed in the
first step. This is unambiguously indicated by the bond
lengths in the ketoimine fragments (Table 2) (average
C–N 1.315, C–C 1.428, and C–O 1.288 Å), which are
intermediate compared to the bond lengths in the neu-
tral [18] and dianionic Dpp-Mian ligands [19]. The
gallium atom in compound VI is pentacoordinated.
Based on the τ parameter calculated from the maxi-
mum angles of the polyhedron O(1)Ga(1)O(2)
(158.04(5)°) and N(2)Ga(1)N(1) (135.66(5)°) being
equal to ~0.4, this polyhedron can be attributed to a
distorted tetragonal pyramid with the iodine atom at
of complex VI was conducted purposefully with
0.5 equiv mol of iodine taken for the reaction.
The further reduction of complex Dpp-Mian
affords compound VII isolated from a violet solution
containing the Dpp-Mian dianion. Since product VII
was not isolated in the crystalline state, its composi-
tion and structure were established by spectral meth-
ods and from an analysis of the structure of the reac-
tion product with phenylacetylene. The reaction of
complex VII with phenylacetylene in toluene at 90°С
completes within 2 h and affords complex VIII iso-
lated in the crystalline state and characterized by
the vertex, since τ = 0 for an ideal tetragonal pyramid X-ray structure analysis.
Ar
N
Ar
N
H
Ph
I
I
Ga
I
O
Ga
O
+2Ph
O
Ga
O
Ga
N
Ar
N
I
Ph
H
Ar
(VII)
(VIII)
Ar = 2,6-diisopropylphenyl
According to the X-ray structure analysis data diimides with anilines [15]. The catalytic tests with the
(Fig. 2), compound VIII is a homochiral dimer: the earlier used substrates were carried out to compare the
catalytic properties of gallium complexes VII and VIII
unit cell contains both R,R- and S,S-enantiomers.
The coordination number of both gallium atoms is 5 as
in the case of complex VI. The τ parameter calculated
for the Ga(1) and Ga(2) atoms is close to 0.5; i.e., the
geometry of the considered tetrahedra is intermediate
between a trigonal bipyramid and a tetragonal pyra-
mid. The structure of the obtained complex VIII has a
number of interesting features. First, the gallium–car-
bon bond of the vinyl fragment is not subjected to pro-
tonolysis with a phenylacetylene excess as it occurs in
complex IV [19]. Second, both ethylenediyl fragments
are arranged at one side of the dimeric molecule,
unlike related digallium complex I. Third, the eth-
ylenediyl fragment links the gallium atom and N,O-
ligand that are not bound to each other, which was
never observed earlier. Selected bond lengths and
bond angles for compounds VI and VIII are presented
in Table 2.
I(1)
O(1)
C(1)
Ga(1)
N(2)
C(26)
O(2)
C(2)
N(1)
C(25)
An unusual property of digallane I is the ability to cat-
alyze the hydroamination [5] and hydroarylation of phe-
nylacetylene [14], as well as the guanylation of carbo-
Fig. 1. Molecular structure of compound VI.
Thermal ellipsoids with 30% probability. Hydrogen atoms
are omitted.
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GALLIUM COMPLEXES WITH ACENAPHTHENE-1-IMINO-2-ONE
385
Table 2. Selected bond lengths (Å) and bond angles (deg) for compounds VI and VIII
Bond
d, Å
Bond
d, Å
VI
Ga(1)–N(2)
Ga(1)–N(1)
Ga(1)–O(1)
Ga(1)–O(2)
Ga(1)–I(1)
O(1)–C(1)
1.984(1)
1.995(1)
2.002(1)
2.010(1)
2.5385(2)
1.287(2)
O(2)–C(25)
N(1)–C(2)
N(2)–C(26)
C(1)–C(2)
C(25)–C(26)
1.278(2)
1.314(2)
1.315(2)
1.430(2)
1.425(2)
VIII
Ga(1)–O(1)
Ga(1)–C(57)
Ga(1)–O(2)
Ga(1)–N(1)
Ga(1)–I(1)
C(57)–C(58)
C(1)–C(26)
C(2)–N(1)
Angle
1.924(3)
1.965(5)
2.169(3)
2.200(4)
2.5226(6)
1.347(7)
1.551(7)
1.275(6)
ω, deg
С(1)–O(1)
1.409(6)
1.921(3)
1.958(5)
2.163(3)
2.202(4)
2.5217(6)
1.317(7)
Ga(2)–O(2)
Ga(2)–C(25)
Ga(2)–O(1)
Ga(2)–N(2)
Ga(2)–I(2)
C(25)–C(26)
Angle
ω, deg
VI
N(2)Ga(1)N(1)
N(2)Ga(1)O(1)
N(1)Ga(1)O(1)
N(2)Ga(1)O(2)
N(1)Ga(1)O(2)
135.66(5)
90.35(5)
83.19(5)
83.21(5)
86.81(5)
O(1)Ga(1)O(2)
N(2)Ga(1)I(1)
N(1)Ga(1)I(1)
O(1)Ga(1)I(1)
O(2)Ga(1)I(1)
158.04(5)
113.00(4)
111.31(4)
100.44(4)
101.40(4)
VIII
O(1)Ga(1)C(57)
N(1)Ga(1)C(57)
O(2)Ga(2)C(25)
C(2)C(1)C(26)
122.4(2)
99.69(18)
123.02(17)
112.6(4)
O(1)Ga(1)N(1)
N(1)Ga(1)I(1)
N(2)Ga(2)C(25)
N(2)Ga(2)I(2)
80.1(1)
104.15(10)
99.92(17)
103.92(11)
based on Dpp-Mian with the properties of digallane I. complex VII showed that the maximum conversion of
The 1H NMR monitoring of the reaction of phenylacet-
the starting components to the hydroamination product
ylene with 4-chloroaniline in the presence of 4 mol % achieved 77% within 48 h at 90°С.
Ph
(VII) or (VIII)
Cl
N
Cl
H +
NH2
Ph
C6D6
These parameters are inferior to those for hydroami- phenylacetylene molecule from complex VIII and the
formation of more catalytically active derivative VII.
Since the catalytic activity of compound VIII turned out
to be low, this compound was not involved in subsequent
catalytic tests.
nation in the presence of digallane I, where the conver-
sion of the starting substances to N-(4-chlorophenyl)-1-
phenylethane-1-imine was 99% within 6 h [5]. Under
similar conditions, the use of 4 mol % compound VIII
exerts no effect on a mixture of the substrates and no
reaction between them occurs. Catalysis is observed only
It has previously been shown that the pheny-
lacetylene adduct of compound I catalyzes the
at 130°С, which is likely related to the elimination of a reaction of 1-naphthol with phenylacetylene:
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386
RAZBOROV et al.
at 45°С within 20 days the hydroarylation product undergoes the Diels–Alder dimerization at ele-
2-(1-phenylvinyl)naphthalen-1-ol is formed in vated temperature [14]. Under the same conditions
70% yield. At 90°С, the reaction proceeds much (90°С) of the reaction of 1-naphthol with pheny-
more rapidly and gives the same product with a lacetylene in the presence of 6 mol % complex VII,
significantly higher yield already within several the yield of 2-(1-phenylvinyl)naphthalen-1-ol
hours. However, the primarily formed product reaches 95% in 20 h.
OH
OH
(VII)
Ph
Ph
H +
C6D6
It is important that the second reaction step
The guanylation of carbodiimides is another exam-
(Diels–Alder cycloaddition) does not occur. Thus, in ple for the hydroamination of unsaturated organic
this case, the use of compound VII is preferable than,
for example, dithiocarbamate complex (Dpp-Bian)-
Ga(S2CNMe2), in the presence of which (2 mol %) at
85°С the hydroarylation product was obtained in 7 h
with a yield that did not exceed 40% [9].
compounds catalyzed by the gallium complexes with
the redox-active Dpp-Bian ligand [15]. We also
showed that compound VII actively catalyzed the
hydroamination of dicyclohexylcarbodiimide by ani-
line.
Cy
HN
Cy
(VII)
C6D6
Cl
NH2
N
C
N
+
C
l
N
NH
Cy
Cy
Cy = cyclohexyl
The conversion of the substrates to the product
reaches 83% at 90°С within 20 h when complex VII
(8 mol %) is added to an equimolar mixture of 4-chlo-
roaniline and dicyclohexylcarbodiimide. These
parameters are comparable to those for the system
including digallane I as a catalyst, although they take
place under more rigid conditions with a larger
amount of the catalyst and within a longer time.
ACKNOWLEDGMENTS
This work was supported by the Russian Science
Foundation, project no. 14-13-01063.
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