Study of the reactivity of organonickel sigma-complexes towards nitriles

Article abstract of DOI:10.1007/s11172-017-1725-8

The reactivity of organonickel sigma-complexes of type [NiBr(Ar)(bpy)], where Ar = 2,6-dimethylphenyl (Xyl), 2,4,6-trimethylphenyl (Mes), 2,4,6-triisopropylphenyl (Tipp), 2,4,6-tricyclohexylphenyl (Tchp), bpy = 2,2′-bipyridine, towards nitriles (acetonitr

Full text of DOI:10.1007/s11172-017-1725-8

Russian Chemical Bulletin, International Edition, Vol. 66, No. 2, pp. 254—259, February, 2017
254
Study of the reactivity of organonickel sigmaꢀcomplexes towards nitriles
Z. N. Gafurov,a,b I. F. Sakhapov,a,b V. M. Babaev,a A. B. Dobrynin,a V. A. Kurmaz,c K. E. Metlushka,a
I. Kh. Rizvanov,a G. R. Shaikhutdinova,a O. G. Sinyashin,a and D. G. Yakhvarova,b
аA. E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843) 273 2253. Еꢀmail: yakhvar@iopc.ru
bA. M. Butlerov Institute of Chemistry, Kazan Federal University,
18 ul. Kremlyovskaya, 420008 Kazan, Russian Federation
cInstitute of Problems of Chemical Physics, Russian Academy of Sciences,
1 prosp. Akad. Semenova, 142432 Chernogolovka, Moscow region, Russian Federation
The reactivity of organonickel sigmaꢀcomplexes of type [NiBr(Ar)(bpy)], where Ar = 2,6ꢀdiꢀ
methylphenyl (Xyl), 2,4,6ꢀtrimethylphenyl (Mes), 2,4,6ꢀtriisopropylphenyl (Tipp), 2,4,6ꢀtricycloꢀ
hexylphenyl (Tchp), bpy = 2,2´ꢀbipyridine, towards nitriles (acetonitrile, propionitrile, chloroaceꢀ
tonitrile, benzonitrile) has been investigated. This reaction leads to imines by formation of new
carbon—carbon bond between aromatic fragment and nitrile group C≡N.
Key words: 2,2´ꢀbipyridine, imines, organonickel sigmaꢀcomplexes, nitriles, mass spectrometry,
Xꢀray analysis, electrosynthesis.
The use of transition metal complexes in catalytic conꢀ
[NiBr(Ar)(bpy)] (Ar is 2,6ꢀdiꢀ or 2,4,6ꢀtriꢀsubstsituted
version of organic compounds is one of the most promisꢀ
ing directions of development in modern chemistry.1 Orꢀ
ganometallic sigmaꢀcomplexes are main intermediates of
catalytic processes involving organic substrates. Applicaꢀ
tion of nickel complexes as catalysts for coupling reacꢀ
tions, leading to the formation of organic and organoꢀ
phosphorus compounds, is actual and of practical deꢀ
mand due to availability and relatively low cost of nickel
derivatives.2 Particular attention has recently been given
to processes based on the use of highly reactive organoꢀ
metallic intermediates, representing the products of the
reaction of organic substrate with an active form of the
metal complex catalyst.3 Such active particles in the proꢀ
cesses of homoꢀ and crossꢀcoupling involving organic
halides are organonickel sigmaꢀcomplexes, which could
be stabilized and isolated in pure form by using orthoꢀ
substituted aromatic halides.4 The substituents in the orthoꢀ
positions of aromatic ring, sigmaꢀbonded with nickel
atom, restrict free rotation around sigma metalꢀcarbon
bond and shield the axial positions of metal center.5 Howꢀ
ever, at present almost no data on the reactivity of orgaꢀ
nonickel sigmaꢀcomplexes towards unsaturated comꢀ
pounds, in particular, to nitriles, are available. At the same
time, the processes of activation and functionalization of
organic derivatives containing carbonꢀnitrogen multiple
bonds in the coordination sphere of the transition metal
complexes have been studied in some detail.6—12
phenyl, bpy is 2,2´ꢀbipyridine) towards nitriles.
Results and Discussion
The series of organonickel sigmaꢀcomplexes 1—4 of
the composition [NiBr(Ar)(bpy)] (Ar is 2,6ꢀdimethꢀ
ylphenyl (Xyl), 2,4,6ꢀtrimethylphenyl (Mes), 2,4,6ꢀtriꢀ
isopropylphenyl (Tipp), 2,4,6ꢀtricyclohexylphenyl
(Tchp)) were prepared according to earlier developed
procedure,13—15 which includes oxidative addition of
electrochemically generated [Ni0(bpy)] complexes to
corresponding aromatic bromides (Scheme 1).
First, it has been experimentally established that by
dissolving of sigmaꢀcomplex 2 in acetonitrile in the abꢀ
sence of intentionally added reagents, capable to decoorꢀ
dinate bromide anion from the coordination sphere of
nickel, the reaction of complex 2 with the solvent
(MeCN) molecules proceeds sufficiently slow (8 h). That
can be judged by the change of the solution color from
intensive red to greenishꢀyellow. This color change is
associated with a cleavage of aryl moiety sigmaꢀbonded
to the nickel atom. The aryl moiety is a ligand of strong
field, and it ensures the realization of lowꢀspin state
(16eꢀcomplex, dsp2ꢀhybridization) of the metal center.2
This is followed by the formation of new carbonꢀcarbon
bond between the aryl moiety and carbon atom of the
nitrile group C≡N.
It was established previously16 that DMF molecules
are capable to substitute the bromide anion in the coorꢀ
The aim of this work is to investigate the reactiꢀ
vity of organonickel sigmaꢀcomplexes of the type
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 0254—0259, February, 2017.
1066ꢀ5285/17/6602ꢀ0254 © 2017 Springer Science+Business Media, Inc.

Reactivity of sigmaꢀcomplexes towards nitriles
Russ.Chem.Bull., Int.Ed., Vol. 66, No.2, February, 2017
255
Scheme 1
Further study of the reactivity of the organonickel
sigmaꢀcomplexes 1—4 towards acetonitrile, propioniꢀ
trile, chloroacetonitrile, and benzonitrile (Scheme 2) was
carried out in DMF—nitrile system, most interesting for
us in terms of the optimization of the overall process. As a
result of all conducted experiments it was established that
the interaction of complexes 1—4 with nitriles 5—8 in the
presence of DMF leads to the formation of imines 9—17
in the solution (see Scheme 2, Table 1). It should be noted
that the final step of the protonation proceeds as the
results of the presence of water traces in the process.
Scheme 2
dination sphere of organonickel sigmaꢀcomplexes with
the formation of cationic complexes which, in turn, can
undergo the reaction of ligand exchange with the moleꢀ
cules of nitriles. Therefore, it was decided to investigate
the interaction of the complex 2 with acetonitrile in the
presence of small amounts of DMF. It turned out that in
this case the solution color change is much faster
(30 min) than in the absence of DMF. This result is of
interest because the use of DMF as a solvent for the
reaction of imines production can allow one to optimize
the whole process with the transition of the conditions to
oneꢀpot synthesis. This is because the electrochemical
The formation of imines 9—17 in the solution was
proved by gas chromatoꢀmass spectrometry. It was found
Table 1. Products of interaction of obtained from organonickel
sigmaꢀcomplexes 1—4 with nitriles 5—8
σꢀComꢀ
R´
R″
Nitrile (R)
plex
generation of organonickel sigmaꢀcomplexes 1—4 is also
5
6
7
8
13—15
successfully carried out in DMF.
In this case the
(Me)
(Et)
(CH2Cl)
(Ph)
isolation and purification in the intermediate steps is not
required. It should be noted that as bromine consuming
reagent boron trifluoride diethyl etherate (BF3•Et2O) can
be used instead of DMF. This allows one to perform the
reaction of imines production in nonpolar organic solꢀ
vents such as benzene, facilitating their separation due to
the precipitation of inorganic nickel complexes.
1
2
3
4
Me
Me
H
Me
9
—*
12
—*
—*
—*
13
—*
—*
10
14
16
11
15
17
Pri
Pri
cycloꢀ
C6H11 C6H11
cycloꢀ
—*
* Not found.

256
Russ.Chem.Bull., Int.Ed., Vol. 66, No. 2, February, 2017
Gafurov et al.
that the reaction of organonickel sigmaꢀcomplex 2 with all
nitriles used in this work yields the corresponding imines
11—14 as the result of addition of Mesꢀfragment of origiꢀ
nal organonickel sigmaꢀcomplex to the C≡N bond
of nitrile molecule. Along the signal of molecular ions
with m/z 161 (11), m/z 175 (12), m/z 195 (13), and m/z
223 (14) the peaks with m/z 146, corresponding to
fragment ions of composition [MesC=NH]+ (or
[C10H12N]+), forming at the elimination of Me, Et,
CH2Cl, and Ph groups from molecular ions of comꢀ
pounds 11—14, respectively, were detected in the mass
spectra of imine series 11—14 (Fig. 1). These compounds
have the same aryl fragment (Mes), but different substiꢀ
tuents R. It should be also noted that the peaks with m/z
160, corresponding to ions [M – CH3]+ and [M – Cl]+,
respectively, are registered in the mass spectra of comꢀ
pounds 12 and 13.
Similar behavior was also registered for the imines 9
(m/z 147), 10 (m/z 209), 15 (m/z 245), 16 (m/z 307), and
17 (m/z 364 [M – H]+). Thus, one may conclude that the
characteristic fragmentation processes for the obtained
imines are the cleavage of αꢀ and βꢀbonds towards sp2ꢀ
hybridized carbon atom of the imine moiety. The cleavage
of the NHꢀgroup under experimental conditions does not
occur. This fragmentation pattern of the molecular ion
confirms the structure of the obtained compounds.
Similar data were obtained for almost all combinaꢀ
tions of organonickel sigmaꢀcomplex—nitrile. A partiꢀ
cularity of the mass spectra of compounds with phenyl
substituent (the imines 10, 14, and 16) is the presence of
more intense peaks of ions [M – H]+ compared with the
peaks of the molecular ion. An analysis of mass spectral
database NIST 1117 and other literature data18 have shown
that the experimentally obtained results reflecting the fragꢀ
mentation mechanism of the imines molecules under conꢀ
ditions of mass spectrometry are in good agreement with
known data obtained previously for the nitrogenꢀcontainꢀ
ing compounds.
To prove the structure and sequence of bonding of the
atoms in the molecules of the synthesized compounds it
has been attempted to isolate one of the imine obtained
in the solution. The imine 11, formed in the reaction of
organonickel complex 2 with acetonitrile, was chosen as
a model compound. The isolation was performed by
column chromatography using ethyl acetate as eluent. As
a result, it was succeeded to isolate the imine 11 with
32% yield.
Irel (%)
146
100
a
161
80
60
129
160
144
130
40
20
105
103
91
162
115
77
65
60
80
100 120 140 160
180
m/z
Irel (%)
100
146
b
80
60
40
20
175
160
143
131
115
91
77
54
105
40
60
100
140
180
220
260 m/z
Irel (%)
100
160
c
146
144
159
80
60
40
20
The imine hydrochloride 11 crystals were obtained
by prolonged storage (over 7 days) of the isolated imine
11 in the chloroform solution and slow evaporation of
the solvent. The structure of crystals was confirmed by
Xꢀray analysis (Fig. 2, Table 2).
Performing the reaction of organonickel sigmaꢀcomꢀ
plex 2 with acetonitrile at temperature 75—80 °C leads to
158
195
143
131
115
91
40
77
197
65
103
40
80
120
160
200
240 m/z
Irel (%)
100
222
223
d
N(1)
80
60
40
20
Cl(1)
C(2)
C(6)
207
206
192
104
116
77 91
97
130
144
C(15)
60
100
140
180
220
260 m/z
Fig. 1. Mass spectra of imine 11 (a), 12 (b), 13 (c), and 14 (d),
obtained from organonickel sigmaꢀcomplex 2.
Fig. 2. Crystal structure of imine hydrochloride 11.

Reactivity of sigmaꢀcomplexes towards nitriles
Russ.Chem.Bull., Int.Ed., Vol. 66, No.2, February, 2017
257
Table 2. Selected bond lengths (d) and valence angles (ω) in
compound 11
Thus, in this study we have shown that the interaction
of the organonickel sigmaꢀcomplexes with the nitriles
results in the formation of the imines of the composition
R(Ar)C=NH (Ar is 2,6ꢀdiꢀ or 2,4,6ꢀtrisubstituted pheꢀ
nyl) containing aromatic moiety from the initial organonꢀ
ickel sigmaꢀcomplex. The obtained results is one of the
first examples of the use of electrochemically generated
organonickel sigmaꢀcomplexes as substrates in organic
synthesis. These results expand the range of possibilities
for the synthetic application of organometallic compounds
of this type.
Bond
d/Å
Angle
ω/degree
C(6)—N(1)
C(6)—C(15)
C(2)—C(6)
1.273(3)
1.489(4)
1.490(3)
N(1)—C(6)—C(2)
N(1)—C(6)—C(15)
C(2)—C(6)—C(15)
120.3(2)
119.9(2)
119.8(2)
the formation of compound 18 in solution. This comꢀ
pound represent the product of the addition of the second
mesityl fragment by nitrogen atom of imine 11. The signals
with m/z 279 and m/z 264, corresponding to molecular
ion [M]+ and the ion [M – CH3]+, formed in the process
of cleavage of methyl group in the condition of experiꢀ
ment, are detected in the mass spectrum of compound 18
(Fig. 3).
Experimental
Experiments related to the preparation of the initial reagents
and preparative electrolysis were carried out under an inert atmoꢀ
sphere (nitrogen) using standard Schlenk technique.
Electron ionisation (EI) mass spectra were obtained using gas
chromatoꢀmass spectrometry with DFS Thermo Electron Corpoꢀ
ration (USA) instrument at electron ionization energy of 70 eV,
temperature of the ion source of 250 °C. Capillary column
IDꢀBPX5 (analogue of DBꢀ5MS) of SGE company with the length
of 60 m and diameter of 0.32 mm was used. The chromatographic
conditions were following: the flow rate of carrier gas (Helium) was
2 mL min–1, injector temperature was 250 °C, initial thermostate
temperature was 160 °C (1 min), heating rate was 20 deg min–1
,
final thermostate temperature was 280 °C (15 min). The data treatꢀ
ment was performed using XСalibur software. 1H and 13С NMR
spectra were registered using high resolution spectrometer Bruker
Avance III 400 at room temperature (25 °C). IR spectra in the range
of 4000—400 cm–1 were measured using Tensorꢀ27 (Bruker) specꢀ
trometer with optical resolution of 4 cm–1 and accumulation of 32
scans. The samples for registration of IR spectra were prepared as
thin layer between two KBr substrates. The centrifugation using
OPNꢀ3.02 (TNK Dastan, Kyrgyzstan) centrifuge at rotation rate
of 1000 min–1 was used for the separation of low dispersity precipiꢀ
tates from the reaction mixture. The column filled with the silica gel
(0.60—0.200 mm, 60 Å) was used for performing column chromaꢀ
tography, eluent was ethyl acetate.
The preparation of some imines described in this study
(9—12, 14, and 16)19—25 and reaction of organonickel
sigmaꢀcomplexes with acetonitrile26 are known in the
literature. However, in all described cases the processes
occur under extreme conditions with the use of inflamꢀ
mable media and involving magnesium and lithium organꢀ
ic reagents, including derivatives obtained from relatively
expensive alkyl iodides. Moreover, the formation of the
imines in the reactions involving organonickel sigmaꢀcomꢀ
plexes requires the use of highly toxic reagents, such as
thallium tetrafluoroborate (TlBF4).26 The method develꢀ
oped here for production of asymmetrical imines in the
reaction of the nitriles with the organonickel sigmaꢀcomꢀ
plexes allows one to avoid completely the use of flammable
media, unstable and toxic reagents.
Imine hydrochloride 11 crystal of suitable for Xꢀray analysis
quality was isolated by crystallization of obtained compound in the
chloroform, the crystals were colorless. Crystals (C11H16N+•Cl–,
M = 197.70) were monoclinic, at 296 K a = 11.469(2), b =
= 8.3584(16), c = 13.328(3) Å, β = 114.814(5)°, V = 1159.7(4) Å3,
Z = 4, space group P21/n, dcalc = 1.132 g cm–3, μ = 0.288 mm–1
,
F(000) = 424. Cell parameters and experimental data were obꢀ
tained at T = 296 K using automatic diffractometer Bruker Smart
APEX II CCD (λ(MoꢀKα) = 0.71073 Å, ωꢀscanning), 2θ < 56°,
Rint = 0.047. 14573 reflections were measured, from them 2738
were independent, the number of observed reflections with I > 2σ(I)
was 1885. The structure was resolved by direct method using SIR27
program and refined by fullꢀmatrix least square method using
SHELXL97 program.28 The hydrogen atoms were calculated geoꢀ
metrically and refined using a riding model. Hydrogen atoms of
NH2ꢀgroup were identified from the series of electron density and
refined in isotropic approximation on the final stage of refinement.
All calculations were performed using program WinGX,29 the final
values of divergence factors were R = 0.0572, wR2 = 0.1699, GOOF
= 1.04, the number of parameters specified was 130. The analysis of
Irel (%)
264
100
80
60
40
279
91
119
20
160
77
146
103
60
100
140
180
220
260
m/z
Fig. 3. Mass spectra of compound 18, obtained from organonickel
sigmaꢀcomplex 2 and acetonitrile.

258
Russ.Chem.Bull., Int.Ed., Vol. 66, No. 2, February, 2017
Gafurov et al.
intermolecular interactions was performed using PLATON proꢀ
gram.30 The figures were prepared in the program MERCURY.31
Crystallographic data of the structure of 11 were deposited into
Cambridge structural database (http://www.ccdc.cam.ac.uk; deꢀ
posit number CCDC 1470168).
Interaction of complexes 1—4 with nitriles 5—8. The interacꢀ
tion was carried out using method B. Complexes [NiBr(Ar)(bpy)],
where Ar = Xyl (80 mg), Mes (83 mg), Tipp (100 mg), and Tchp
(124 mg), and nitriles (MeCN, EtCN, ClCH2CN, and PhCN)
were used as starting compounds. The obtained reaction mixture
was analyzed by gas chromatoꢀmass spectroscopy without addiꢀ
tional treatment. Retention times (tR) and m/z peaks values, detectꢀ
ed in EI mass spectra of the obtained compounds are represented
below.
1ꢀ(2,6ꢀDimethylphenyl)ethanimine (CH3(Xyl)C=NH) (9).
MS (EI, 70 eV, tR = 6.80 min), m/z (Irel (%)): 147 [M]+ (58), 133
[M – CH3]+ (44), 129 (33), 115 (42), 105 (27), 91 (51), 77 (40),
65 (23).
1ꢀ(2,6ꢀDimethylphenyl)ꢀ1ꢀphenylmethanimine (Ph(Xyl)C=NH)
(10). MS (EI, 70 eV, tR = 6.15 min), m/z (Irel (%)): 209 [M]+ (25),
208 [M – H]+ (100), 194 (11), 193 (28), 121 (13), 105 (23), 77 (49).
1ꢀ(2,4,6ꢀTrimethylphenyl)ethanimine (CH3(Mes)C=NH) (11).
MS (EI, 70 eV, tR = 4.72 min), m/z (Irel (%)): 161 [M]+ (80),
160 (52), 146 [M – CH3]+ (100), 145 (26), 144 (37), 131 (33),
130 (36), 129 (43), 105 (24), 91 (23), 77 (20).
Dimethylformamide was purified by triple vacuum distillation
with intermediate drying over calcium hydride (10 g L–1) and was
stored in the nitrogen atmosphere. Acetonitrile was purified by
triple distillation in inert atmosphere with addition of small amount
of potassium permanganate. Ethyl acetate was purified by subseꢀ
quent distillation over phosphor pentoxide (Р2О5), then potassium
carbonate (K2CO3) to remove acidic admixtures. Organic subꢀ
strates, namely chloroacetonitrile (Alfa Aeser), propionitrile, benꢀ
zonitrile, and 2,2´ꢀbipyridine (SigmaꢀAldrich) were used as reꢀ
ceived. Complex [NiBr2(bpy)], used for preparation of organonickꢀ
el sigmaꢀcomplexes, was prepared from nickel(II) bromide and 2,2´ꢀ
bipyridine as described earlier.32 Organonickel sigmaꢀcomplexes
1—4 were prepared according to earlier published procedures13—15
in the electrolyzer of the periodic loading, without separation of the
anodic and cathodic areas, equipped with sacrificial nickel anode.33
Interaction of complex [NiBr(Mes)(bpy)] (2) with acetonitrile
(5). Method A. The working solution was prepared by dissolving of
180 mg (0.43 mmol) of complex [NiBr(Mes)(bpy)] in 11 mL of
acetonitrile at room temperature. The solution was stirred for 8 h.
During the reaction, simultaneously with the change in color of the
solution from bright red to greenishꢀyellow fine precipitate formaꢀ
tion occurred in the reaction mixture. The precipitate was separated
by centrifugation. Decanted solution was evaporated at water pump
vacuum at a bath temperature of 30 °C. The resulting residue was
chromatographed using silica gel column with ethyl acetate as
eluent. Two fractions were obtained. TLC (Sorbfil, eluent was ethyl
acetate): Rf = 0.82 (mass spectra peaks m/z 264 and 279) and Rf =
= 0.50 (mass spectra peak m/z 162.1). The yield of the imine 11 was
21 mg (32%). To determine the composition and structure of the
obtained product the following methods were used: gas chromatoꢀ
mass spectrometry, 1Н and 13С NMR spectroscopy, IR spectroscopy.
1ꢀ(2,4,6ꢀTrimethylphenyl)ethanimine (CH3(Mes)C=NH) (11).
1Н NMR (400 MHz, CDCl3, δ): 2.21 (s, 6 H, C(9)Me, C(11)Me);
2.24 (s, 3 H, C(10)Me); 2.35 (s, 3 H, C(1)Me); 6.91 (s, 2 H,
C(5)H, C(7)H). 13С NMR (100.6 MHz, CDCl3, δ): 20.57
(C(1)Me); 23.70 (2, C(9)Me, C(11)Me); 29.72 (C(10)Me); 129.03
(C(3)); 129.11 (2, C(5), C(7)); 136.29 (C(6)); 137.90 (2, C(4),
C(8)); 147.93 (C(2) CN). MS (EI, 70 eV, tR = 4.72 min), m/z
(Irel (%)): 161 [M]+ (82), 160 (54), 146 [M – CH3]+ (100), 145
(25), 144 (35), 131 (35), 130 (37), 129 (42), 105 (26), 91 (25), 77
(22). IR (neat), ν/cm–1 3251 (N—H); 2923, 2854 (CH3); 1641
(N=С); 1611 (C=Сarom).
1ꢀ(2,4,6ꢀTrimethylphenyl)propanimine (C2H5(Mes)C=NH)
(12). MS (EI, 70 eV, tR = 6.23 min), m/z (Irel (%)): 175 [M]+ (41),
160 [M – CH3]+ (31), 146 [M – C2H5]+ (100), 143 (26), 131 (20),
91 (15).
1 ꢀ ( 2 , 4 , 6 ꢀ T r i m e t h y l p h e n y l ) ꢀ 2 ꢀ c h l o r o e t h a n i m i n e
(ClCH2(Mes)C=NH) (13). MS (EI, 70 eV, tR = 6.90 min) m/z (Irel
(%)): 195 [M]+ (57), 160 [M – Cl]+ (100), 159 (81), 158 (66), 146
[M – CH2Cl]+ (86), 145 (43), 144 (76), 143 (41), 130 (37), 115
(32), 91 (25), 77 (19).
1ꢀ(2,4,6ꢀTrimethylphenyl)ꢀ1ꢀphenylmethanimine
(Ph(Mes)C=NH) (14). MS (EI, 70 eV, tR = 6.75 min), m/z (Irel (%)):
223 [M]+ (26), 222 [M – H]+ (100), 208 (11), 207 (34), 206 (18),
192 (7), 104 (10), 91 (7), 77 (8).
1ꢀ(2,4,6ꢀTriisopropylphenyl)ethanimine (CH3(Tipp)C=NH)
(15). MS (EI, 70 eV, tR = 7.42 min), m/z (Irel (%)): 245 [M]+ (21),
231 (27), 230 [M – CH3]+ (100), 229 (29), 214 (42), 186 (16),
172 (13), 157 (12), 143 (15), 129 (14).
1ꢀ(2,4,6ꢀTriisopropylphenyl)ꢀ1ꢀphenylmethanimine
(Ph(Tipp)C=NH) (16). MS (EI, 70 eV, tR = 6.89 min), m/z (Irel (%)):
308 (15), 307 [M]+ (63), 306 [M – H]+ (100), 292 (19), 291 (23),
276 (14), 275 (24), 247 (19), 233 (15), 232 (15), 230 (18), 218 (9),
104 (19), 91 (12).
1ꢀ(2,4,6ꢀTricyclohexylphenyl)ethanimine (CH3(Tchp)C=NH)
(17). MS (EI, 70 eV, tR = 13.10 min), m/z (Irel (%)): 364 [M – H]+ (9),
350 [M – CH3]+ (100), 348 (51), 333 (21), 308 (9), 265 (23), 183 (20).
N , 1 ꢀ B i s ( 2 , 4 , 6 ꢀ t r i m e t h y l p h e n y l ) e t h a n i m i n e
(CH3(Mes)C=NMes) (18). MS (EI, 70 eV, tR = 8.14 min), m/z
(Irel (%)): 279 [M]+ (23), 264 [M – CH3]+ (100), 160 (11), 146 (7),
119 (11), 103 (7), 91 (15), 77 (8).
Preparation of imine hydrochloride 11. Under long (more than
7 days) storage of 21 mg of isolated using method A imine 11 in
chloroform solution (5 mL) and slow evaporation of solvent, small
amount of imine hydrochloride 11 was obtained. Its molecular
structure was determined by single crystal Xꢀray analysis (see
Fig. 2). Found (%): С, 66.71; Н, 8.57; N, 6.98. С11ClH16N.
Calculated (%): С, 66.83; Н, 8.16; N, 7.08.
Method B. The working solution was prepared by dissolving of
83 mg (0.2 mmol) of complex [NiBr(Mes)(bpy)] in 2 mL of
acetonitrile at room temperature. Then 2—3 drops of DMF were
added to the solution. After stirring for 30 min the obtained reaction
mixture was analyzed without additional treatment by gas chromaꢀ
toꢀmass spectroscopy.
Method C. The working solution was prepared by dissolving of
83 mg (0.2 mmol) of complex [NiBr(Mes)(bpy)] in 20 mL of
benzene at room temperature. The 21 μL (0.4 mmol) of acetonitrile
was added to the solution. Afterwards, 49 μL (0.4 mmol) of boron
trifluoride diethyl etherate (BF3•Et2O) was added and immediate
discoloration of solution was observed. After stirring for 30 min the
formed turquoise precipitate was separated by filtration and the
filtrate was analyzed by gas chromatoꢀmass spectroscopy.
This work was financially supported by the Russian
Foundation for Basic Research and the Government of
Tatarstan in the framework of scientific project No. 15ꢀ
43ꢀ02667.

Reactivity of sigmaꢀcomplexes towards nitriles
Russ.Chem.Bull., Int.Ed., Vol. 66, No.2, February, 2017
259
17. NIST/EPA/NIH Mass Spectral Library with Search Program,
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Received November 16, 2015;
in revised form March 25, 2016