Single-stage synthetic route to perfluoroalkylated arenes via electrocatalytic cross-coupling of organic halides using Co and Ni complexes

Article abstract of DOI:10.1016/j.jorganchem.2016.08.003

A new method of single-stage synthesis of perfluoroalkylated arenes via cross-coupling of bromo (in some cases, chloro) arenes and heteroarenes (derivatives of benzene, pyridine and furan) and organic perfluoroalkyl halides involving complexes of nickel and cobalt in low oxidation state with α-diimines under mild conditions was proposed. Perfluoroalkylated products are obtained in good yields in the presence of М(I)L (M?=?Ni, Co) catalyst (1–10%) electrochemically generated from M(II)L at room temperature without chemical reductant. It has been found that success of the catalytic process is dependent on the reduction potential of the catalyst. The more negative reduction potential is, the more effective is the catalyst.

Full text of DOI:10.1016/j.jorganchem.2016.08.003

Journal of Organometallic Chemistry 820 (2016) 82e88
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Single-stage synthetic route to perfluoroalkylated arenes via
electrocatalytic cross-coupling of organic halides using Co and Ni
complexes
Mikhail Khrizanforov*, Vera Khrizanforova, Vahid Mamedov, Nataliya Zhukova,
Sofia Strekalova, Valeriya Grinenko, Tatyana Gryaznova, Oleg Sinyashin, Yulia Budnikova
A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of Russian Academy of Sciences, 8 Arbuzov Str., 420088, Kazan, Russian
Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
A new method of single-stage synthesis of perfluoroalkylated arenes via cross-coupling of bromo (in
Received 29 October 2015
Received in revised form
30 July 2016
Accepted 1 August 2016
Available online 3 August 2016
some cases, chloro) arenes and heteroarenes (derivatives of benzene, pyridine and furan) and organic
perfluoroalkyl halides involving complexes of nickel and cobalt in low oxidation state with
under mild conditions was proposed. Perfluoroalkylated products are obtained in good yields in the
presence of
a-diimines
М
(I)L (M ¼ Ni, Co) catalyst (1e10%) electrochemically generated from M(II)L at room tem-
perature without chemical reductant. It has been found that success of the catalytic process is dependent
on the reduction potential of the catalyst. The more negative reduction potential is, the more effective is
the catalyst.
Keywords:
Perfluoroalkylation
Fluorine
© 2016 Published by Elsevier B.V.
Copper
Cross-coupling
Radical reactions
1. Introduction
Although the involvement of transition metals to affect per-
fluoroalkylation reactions has in the past relied on the employment
Perfluoroalkyl arenes gradually become essential for the phar-
maceutical and agrochemical industry materials [1].
of costly organocatalysts and/or harsh reaction conditions, alter-
native metal-mediated perfluoroalkylation strategies of organic
substrates have been sought.
An important issue in synthetic chemistry is the development of
methods for the introduction of fluoroalkyl substituents into
different molecules, particularly at late stages of the synthesis of
complex structures. In the literature, the perfluoroalkylation reac-
tion is classified according to the nature of fluoroorganic particles
as radical (RF.), nucleophilic (RFꢀ), and electrophilic (RFþ), but this
classification is arbitrary, because the reactivity of, for example,
compounds with metal fluoroalkyl bonds may be ambiguous, and
they are often referred to as radical or nucleophilic reagents.
Methods for appending of these groups are discussed in numerous
publications, including monographs and reviews [2].
A challenge is to find a new, less expensive catalyst that can
operate under mild conditions. Little attention has been paid to the
creation of universal soluble reactive organometallic precursors
that could operate rapidly and quantitatively in catalytic synthesis
at the room temperature without the formation of byproducts that
could diminish catalytic performance in the overall process. In
many cases, homogeneous catalysis of electrochemical reactions
involving transition metal complexes overcomes the limitations
and disadvantages of classical methods in terms of its ability to
facilitate the study of reaction mechanisms and synthetic applica-
tions. There have been several examples of catalytic fluo-
roalkylation in recent years [4].
Perfluoroalkylation reactions of aryl bromides that are more
commercially and synthetically available than aryl iodides have
been limited to substrates containing electron-withdrawing groups
[2e]. There is a single report of the trifluoromethylation of aryl
chlorides with Pd [5i]. However, these reactions require an
Despite the long history of fluoroalkylation methods and various
fluoroalkylating reagents, such reactions have until recently tended
to use stoichiometric amounts of starting reagents or even an
excess of them. There were almost no catalytic reactions [2,3].
* Corresponding author.
E-mail address: khrizanforov@gmail.com (M. Khrizanforov).
http://dx.doi.org/10.1016/j.jorganchem.2016.08.003
0022-328X/© 2016 Published by Elsevier B.V.

M. Khrizanforov et al. / Journal of Organometallic Chemistry 820 (2016) 82e88
83
expensive palladium pre-catalyst, ligand and CF3 source.
nickel and cobalt in a different ligand environment (Fig. 1).
Electrochemical reactions have advantages enabling easy con-
trol of the process conversion rate and (within certain limits)
selectivity using parameters such as current density and potential
that allow to vary catalytic activity of the reduced form of metal
complex [4a,5]. Electrochemistry provides advantageous methods
for synthetic purposes as well as for mechanistic investigation.
Electrosynthesis is useful in transition metal catalysis as a means
for generating the active catalyst form without addition of oxidizing
or reducing agents. When performed in mild conditions, it offers
environmentally non-polluting alternatives to traditional organic
synthesis. There are various successful examples of electrochemical
fluoroalkylation reactions [4a,5].
The above-mentioned important goal is to search for new cat-
alytic reactions of aromatic fluoroalkylation including electro-
chemical type, to establish general regularities of electrochemical
processes and factors that determine the reactivity of the catalyst
and direction of bond opening (or formation), and to determine
factors stabilizing (facilitating) or hindering the process. Of
particular interest is the use of cheap common metals such as
nickel, cobalt and others, as well as bromine and chlorinated de-
rivative arenes (heteroarenes) that rarely successfully transform.
We attempted to solve a number of interrelated tasks, namely to
demonstrate the possibility of electrocatalytic aromatic fluo-
roalkylation of bromines and bromine heteroarenes under mild
conditions by selecting the most efficient, affordable catalysts, i.e.,
complexes of nickel and cobalt with different ligands, in order to
optimize the process in an electrochemical cell with different sol-
uble and insoluble anodes and to set a pattern of cross-coupling
and factors that would influence the outcome.
It has been found that the joint electrolysis of metal complexes
MX2L (M ¼ Ni, Co; L ¼ 2,20-bipyridine (bpy), 2,20:60,200terpyridine
(tpy), 2,9-dimethyl-1,10-phenanthroline (dmphen), 4,40-di-tert-
butyl-2,20-bipyridine (dtbpy), 1H,10H-2,20-bibenzo[d]imidazole
(dbi), 2-(1H-benzo[d]imidazol-2-yl)-3-phenylquinoxaline (bipq),
5-(1H-benzo[d]imidazol-2-yl)-6-phenylpyrazine-2,3-
dicarbonitrile (bippdcn)) in the presence of bromobenzene and
C6F13I in DMF in undivided electrolytic cell leads in some cases to
cross-coupling products Ph-Rf with a good yield (Scheme 1). Re-
action proceeds with the catalytic regeneration of M(I)L at the first
peak potential of catalytic regeneration (Table 1).
It should first be noted that the combination of bromobenzene
and perfluoroalkyl iodide could be carried out at room temperature
under catalytic conditions. Previously, the best results were re-
ported by Vicic [4b] and Hartwing [4c], as discussed in papers
reporting aryl bromide reaction with copper (I) [(Phen)CuCF3] at a
temperature above 65ꢁC, copper was taken in stoichiometric
instead of catalytic quantities.
It is important that the reaction between phenyl chloride and
iodine perfluorohexane, when using [CoCl2dtbpy] complex as the
catalyst (aryl substrate: alkyl-substrate: catalyst ¼ 1:1:0.1) with a
MX2L, 2F
PhBr + C6F13
I
C6F13 - Ph
X= Cl, Br
Ph
H
DMF,
room temperature
The anode: Cu, Zn, Mg;
M=Ni or Co;
L:
N
N
N
N
N
N
N
N
2. Results and discussion
bipq
bpy
dmphen
Ph
H
H
N
H
N
N
N
We selected various complexes with nitrogen-containing li-
gands for electrochemical catalytic reactions that are known to
stabilize the low-oxidation-state metals. For example, we used a-
CN
N
N
N
N
N
N
dbi
bippdcn
CN
dtbpy
diimine compound (bpy, tpy, dmphen, dtbpy), which has been
extensively studied in electrochemistry and is used in variety of
catalytic reactions, and substituted imidazole (dbi, bipq, bippdcn),
which had not been studied in detail before, but could be useful in
these processes and facilitate understanding of the factors that
affect success of cross-coupling. The reactions use a complex of
Scheme 1. It has been found that the most effective catalysts are complexes of nickel
and cobalt with bpy, dbi, dtbpy and dmphen ligands in the presence of a copper anode
(Table 2). It has been previously demonstrated in detail using the example of cross-
combination of PhI and C6F13I [5b]. Thus, the conducted reactions revealed a deci-
sive influence of metal pair catalyst complex and soluble anode metal. It allows to
assume that the transmetalation step plays key role in the catalytic cycle [5b].
Fig. 1. Reaction path for Py-Br þ C6F13I catalyzed by 10% of [CoCl2dtbpy]: a) start of reaction, blue color of reaction mixture; b) after passing of 1F electricity, green color of reaction
mixture; c) after passing of 2F electricity, yellow color of reaction mixture. (For interpretation of the references to colour in this figure legend, the reader is referred to the web
version of this article.)

84
M. Khrizanforov et al. / Journal of Organometallic Chemistry 820 (2016) 82e88
Table 1
with an equimolar amount of 3-bromopyridine for 40 h, thereby
attaining a yield of 71% [6].
In this paper, the best yield of 2-perfluoro-n-hexyl pyridine
(72% 2%) was achieved with [СoCl2dbi] (10%) through combina-
tion of 2-bromopyridine and C6F13I at 25 ꢁC in the presence of
copper anode.
First peak reduction potentials of metal complexes MX2L (X ¼ Cl, Br) used for flu-
oroalkylation reaction. Conditions: GC working electrode, DMF, room temperature. n
e number of electrons.
L
ꢀЕ1pred, V (n)
Ni(II) bromide
Co(II) chloride
In the absence of М(II)
The reaction of 2-bromo furan and perfluoro-n-hexyl iodide
using copper anode with catalyst [CoCl2dbi] (10%) or [CoCl2dtbpy]
(10%) at the room temperature (21 ꢁC) results in the high yield of
cross-coupling product (71%).
ꢀ
ꢀ
ꢀ
bpy
1.12 (2e)
1.19 (1e)
1.85 (1e)
ꢀ
ꢀ
ꢀ
dtbpy
dmphen
dppe
bippdcn
dbi
1.34 (2e)
1.22 (1e)
1.96 (1e)
ꢀ
ꢀ
ꢀ
1.35(2e)
1.39 (1e)
2.12 (1e)
ꢀ
ꢀ
ꢀ
1.37 (1e)
1.42 (1e)
2.10 (1e)
ꢀ
ꢀ
ꢀ
0.73 (2e)
0.75 (1e)
0.81 (1e)
The reaction of 3-bromothiophene with perfluoro-n-hexyl
bromide or perfluoro-n-hexyl iodide or 1-bromo-1H,1H,2H,2H-
perfluorodecan under electroreduction conditions with the studied
catalysts does not result in a cross-coupling product (Scheme 2).
The result of this reaction is a polymerization product mixture with
high molecular weight. Thus, it was impossible to get fluoroalkyl-
substituted derivative of 3-bromothiophene. The reactivity of 2-
substituted aromatic substrates (2-bromopyridine, 2-bromofuran)
in the studied catalytic perfluoroalkylation was observed previ-
ously [6] and the propensity for oligomerization and polymeriza-
tion of 3-bromothiophene in electrochemical processes is already
known [7].
ꢀ
ꢀ
ꢀ
1.53 (4e)
1.72 (4e)
1.69 (1e)
ꢀ
ꢀ
ꢀ
bipq
bpym
0.75 (1e)
0.65 (1e)
1.34 (1e)
ꢀ
ꢀ
ꢀ
1.34 (2e)
1.27 (1e)
1.99 (1e)
Ref. el.: Ag/AgCl, 10ꢀ2 M, Сcompounds ¼ 5 mM.
E
1/2 of Fc/Fcþ ¼ 0.45 V vs. Ag/AgCl.
copper anode, gives yields of cross-coupling products around 50%.
This is somewhat inferior to the results of the Cho method for
palladium-catalyzed trifluoromethylation of aryl chlorides [4d], but
our proposed approach is realized under mild conditions with more
accessible, less costly catalyst (cobalt versus palladium and dtbpy
versus BrettPhos).
Joint electrolysis of 4-bromobenzonitrile and perfluoro-n-hexyl
iodide (1:1) at room temperature (23 ꢁC) with a copper anode in the
presence of catalyst СoCl2dbi (10%) or [СoCl2dtbpy] (10%) resulted
in a cross-coupling product 4-perfluoro-n-hexyl benzonitrile with
high yields of 89% and 85%, respectively. High yield of cross-
coupling product is provided in this case due to the electron
withdrawing properties of nitrile groups that increase Aryl-Hal
bond length through pulling of the electron density, increase its
reactivity with respect to the M(I)L, and probably also promotes
reductive elimination stage, which is considered to be the slowest
stage of the catalytic cycle. Similar observations were made, for
example, by Togni (alkylation through nucleophilic substitution
mechanism) [8] and Yu (alkylation through radical mechanism) [9].
It is found that electron-donating substituents in the molecule
of aryl halide prevent cross-coupling of aryl halides and per-
fluorylalkyl halides, as it was previously observed [2e,8]. Thus,
under electric reduction conditions reaction of perfluoroalkyl ha-
lides with 1-bromo-4-methoxyphenyl or 4-bromoaniline does not
give the cross-coupling product with any of the catalysts.
Joint electrolysis of bromo-mesityl with perfluoro-n-hexyl
iodine in the presence of [CoCl2dtbpy] (10%) complex gives the
cross-coupling product with yield of 44%. Apparently, this is a lower
yield in comparison with phenyl bromide due to the steric factor,
namely congestion of the orthogonal position of the aromatic ring
Thus, in order to expand the range of possible substrates for
effective fluoroalkylation evaluation, we selected individual rep-
resentatives of aromatic and heteroaromatic halides (Scheme 2).
It has been found that the reaction of halide pyridines with
perfluoroalkyl halides in the presence of catalytic amounts of Co
and Ni complexes (SI) results in cross-coupling of products with
good yields (up to 72%). These products were obtained through
catalytic synthesis for the first time.
Accordingly, the joint electrolysis of 3-bromopyridine and C6F13
I
(1:1) in the presence of some complexes of Ni or Co (10%) after
passing 2F electricity in DMF at potential of the first reduction peak
of the metal complex in a cell with a copper anode gives cross-
coupling products with yields ranging from 60% to 70%. The best
yield of 3-perfluoro-n-hexylpyridine (71%) was achieved with the
catalyst [СoCl2dbi] at 24ꢁС with copper anode. In the Cheng paper,
3-perfluoro-n-hexylpyridine was prepared in two stages: the first
was synthesis of Cu-RF derivative by stirring perfluoro-n-hexyl io-
dide (1 equiv.) with bronze chips (2 equiv.) over 30 min at a tem-
perature of 125e135 ꢁC, and the second was obtaining of the cross-
coupling product through reaction with organocopper reagents
Rf
CH3
Rf
of the substrate, which leads to increased resistance of s- organic
H3C
metal complexes (key reagents of the catalytic cycle) and low
reactivity [10].
N
Rf
CH3
CH3
Rf
During reaction, the reaction mixture undergoes a double color
change, which may correspond to different forms of metal complex
catalysts or intermediates of the catalytic cycle [5b].
According to the diagram of dependency between the yield of 2-
perfluoro-n-hexyl pyridine and the electrolysis time, it can be
Rf
M2+L + e
Aryl-X + RFX
M = Ni or Co;
O
ꢀ
assumed that the first stage (1e) includes binding of a metal with
Rf
perfluoroalkyl halide through reaction of oxidative addition with
L = bpy, dbi, bipq,
formation of green sigma complex of cobalt (here cross-coupling
bippdcn, dtbpy, dmphen
ꢀ
N
product is absent according to chromatography results), then (2e)
Rf
Rf
Rf
the metal reacts with the aromatic partner in the presence of cross-
coupling product and sigma-copper complex (Figs. 1 and 2).
Thus, we developed an effective method of electrocatalytic
cross-coupling of fluoroalkyl and aryl halides and tested it with a
variety of anode metals and catalysts.
Rf
S
CN
OCH3
NH2
The advantages of this method are following: cross-coupling
proceeds successfully not only with iodo- [5b], but also with
Scheme 2. The range of products produced by the electrochemical reaction of cross-
coupling with selected catalysts. Aryl-X (X ¼ Br, Cl), RFX ¼ C6F13I.

M. Khrizanforov et al. / Journal of Organometallic Chemistry 820 (2016) 82e88
85
Fig. 2. Diagram of yields of cross-coupling products, Py-Br þ C6F13I ¼ Py-C6F13 for different catalysts and electrolysis times (number of transferred electrons).
bromo-aromatic substrates and perfluoroalkyl halide; it is a single-
stage catalytic method characterized by mild conditions and room
temperature. It was possible to carry out the reaction even with
chlorobenzene, albeit with lower yields.
oxidative addition step rate, which is a determining factor in the
catalytic cycle. In any case, exactly these catalysts allowed to bal-
ance the main steps of the catalytic cycle, oxidative addition, and
reductive elimination for the overall process.
The most effective cross-coupling process is with 4-
bromobenzonitrile,
2-bromofuran,
2-bromopyridine,
2-
3. Experimental section
chloropyridine, 3-bromopyridine and with perfluoro-n-hexyl io-
dide, perfluoro-n-hexyl bromide or 1-bromo-1H,1H,2H,2H-per-
fluorodecan. Thus, the proposed method is effective in case of
aromatic substrates with different characteristics. The most effec-
tive catalysts are complexes characterized by negative reduction
potential, specifically [CoCl2bpy] [CoCl2dtbpy], [CoCl2dbi],
[CoCl2dmphen], [NiBr2bpy], [NiBr2tpy] and [NiBr2dbi].
Supplementary Information (SI) available: Text, synthesis and
electrosynthesis conditions, physicochemical characteristics of
catalysts and products.
3.1. General procedures
The cross-coupling product yield is therefore dependent on the
reduction potential of the metal-catalyst complex (under the same
conditions). Thus, all the data concerning potentials and yields on
the example of phenyl bromide and perfluoro-n-hexyl iodide cross-
coupling are given in Table 3. A plot of yield (%) vs reduction po-
tential (V) of the catalyst is almost linear, with the correlation co-
efficient equal to 0.9236 (see Fig. 3).
Success of the catalytic process is therefore dependent on the
catalyst reduction potential. The more negative the reduction po-
tential is, the more effective will be the catalyst. There is no simple
explanation for this factor, but perhaps more negative reduction
potential determines the greater force of the reducing agent and
All reactions were carried out under dry argon atmosphere. All
solvents employed were purified and dried prior to use. N,N-
Dimethylformamide was purified through double fractionation
distillation over melting potash. Perfluoroiodohexane, per-
fluorobromohexane, 10-bromo-1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hepta
decafluorodecane were purchased from P&M Invest and used
without further purification. Benzene, 2-bromofuran, 4-
bromobenzonitrile,
2-chloropyridine,
2-bromo-1,3,5-trimet
hylbenzene, 3-bromothiophene, 1-bromo-2-methylbenzene, 1-
bromo-4-methoxybenzene, 3-bromopyridine, 2-bromopyridine,
bromobenzene, 4-bromoaniline, 2,20:60,200terpyridine, 2,9-dimet
hyl-1,10-phenanthroline, 4,40-di-tert-butyl-2,20-bipyridine were
procured from Acros Organics. Tetraethylammonium tetra-
fluoroborate was purchased from Aldrich and recrystallized from
diethylether. CoCl2*6H2O (97%), NiBr2*3H2O (98%) and 2,20-bipyr-
idine (99 þ %, all from Alfa Aesar) were used without further pu-
rification. Preparative electrolysis was performed by means of
direct current source B5e49 in thermostatically controlled cylin-
drical divided electrolyser (100 ml, three-electrode cell). Platinum
with surface areas of 20 cm2 was used as cathode; platinum rod
was used as anode. The working electrode potential was deter-
mined using reference electrode Ag/AgCl. During electrolysis, the
electrolyte was stirred with a magnetic stirrer. A saturated solution
of Et4NBF4 in DMF was used as anolyte, and cathode and anode
spaces weren't separated by a ceramic membrane, except for Pt-
anode. Mass spectra were recorded in EI mode using Thermo-
Quest TRACE MS. IR spectra of the compounds were recorded on
FTIR spectrometer ‘‘Vector 22’’ (Bruker) in the 400e4000 cmꢀ1
range and on FTIR spectrometer IFS 113v (Bruker) in the
100e600 cmꢀ1 range with resolution of 1 cmꢀ1. Solid samples
were prepared with KBr, respectively.
Fig. 3. The dependence of reaction yield (PhBr þ C6F13I ¼ C6F13-Ph) from potential of
the first reduction peak of the complex.

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M. Khrizanforov et al. / Journal of Organometallic Chemistry 820 (2016) 82e88
Table 3
3.2. NMR experiments
The yield of cross-coupling product and reduction potential MX2L at room
temperature.
NMR investigation was carried out in the NMR department (A.E.
Arbuzov Institute of Organic and Physical Chemistry) of the Federal
Collective Spectral Analysis Center for physical and chemical in-
vestigations of structure, properties and composition of matter and
materials. NMR experiments were carried out with Bruker spec-
MX2L
ꢀЕ1pred, V
Yields of Ph-C6F13 from PhBr and C6F13I, %
[CoCl2bipq]
[NiBr2bippdcn]
[NiBr2bipq]
[CoCl2bippdcn]
[CoCl2bpy]
[NiBr2bpy]
[CoCl2dtbpy]
[NiBr2tpy]
0.65
0.73
0.75
0.84
1.29
1.13
1.22
1.30
1.39
1.54
1.72
30
31
31
37
78
75
82
73
80
75
85
trometers AVANCE-400 (400.1 MHz (1H), 376.5 MHz
(
19F),
100.6 MHz (13C)) and AVANCE-600 (600.1 MHz (1H), 150.9 MHz
(
13C)) equipped with a pulsed gradient unit capable of producing
magnetic field pulse gradients in the z-direction of 53.5 G cmꢀ1. All
[CoCl2dmphen]
[NiBr2dbi]
[CoCl2dbi]
spectra were acquired in a 5 mm gradient inverse broad band probe
head. Chemical shifts are reported in the
d (ppm) scale relative to
the residual 1H and 13C signal of C6D6 and to external C6F6
(ꢀ164.9 ppm) for 19F NMR spectra.
3.3.2. 1,3,5-Trimethyl-2-(perfluorohexyl)benzene (2)
m.t.>300ꢁС. 1Н NMR (400 MHz, CDСl3):
¼ 2,17 (s, 9H, CH3),
6,86 (s, 2H, H). 19F NMR (376 MHz, C6D6):
¼ ꢀ81,92 (3F, t,
d
3.3. Results of coupling reaction of organic halides
d
J ¼ 9.8 Hz), ꢀ110,8 (2F, t, J ¼ 14.6 Hz). ꢀ121,27 (br.s., 2F,
CF2), ꢀ123,58 (br.s, 2F, CF2), ꢀ123,8 (br.s., 2F, CF2), ꢀ127,8 (br.s., 2F,
A solution for electrolysis was prepared by mixing of (9.7 mmol)
arene, (9.7 mmol) fluorosubstrate and 0.97 mmol of catalyst MX2L
in DMF (70 ml). Electrolysis was carried out in undivided electro-
chemical cell at ambient temperature under argon atmosphere at
the potential of working electrode corresponding to reduction po-
tential of the complex from Table 2. The amount of electricity
CF2). 13C NMR (100,6 MHz, CDСl3):
d
¼ 19,64 (CH3), 21,11 (CH3),
109,48 (C5), 112.08 (C4,C3), 118.51 (CF3), 127.77 (C9), 136.17 (C8). IR
(KBr,
n
, cmꢀ1): 1151, 1201, 1237 (CeF), 1602, 1503 (C¼Carom), 3071
(CHarom), 2954 (СН3). EIMS, m/z: 438,03þ[М
] ,
þꢃ,167,05 [C3F6eCH3]þꢃ
148,03 [C3F6eH]þꢃ, 118,05 [C2F4eCH3] ꢃ, 103,11 [C2F4eH]þ, 91,01
[C7H7]þꢃ. Found (%): C: 41,00; H: 2,48. C15H11F13. Anal. calc. (%): C,
41.11; H, 2.53; F, 56.36.
passed through the electrolyte were 2F per
1 mol of per-
fluoroiodohexane (520 mA ꢂ hꢀ1). After completing the electrol-
ysis, the solution was washed with distilled water (100 ml) and
extracted with benzene (3 ꢂ 100 ml). The organic layer was dried
over magnesium sulfate and filtered. The residual solution was
concentrated. The reaction mixture was filtered through a plug of
silica (eluated with 5% EtOAc: 95% hexane). The filtrate was
concentrated, and the product was isolated (isolated yield in
Table 1_SI).
3.3.3. 1-methyl-2-(perfluorohexyl)benzene (3)
b.p. 218ꢁС. 1Н NMR (400 MHz, CDСl3):
d
¼ 2,36(s, 3H, CH3),
7,12e7,45 (m, 4H, H). 19F NMR (376,5 MHz, C6D6):
d
¼ ꢀ81,92 (s, 3F,
CF3), ꢀ106,92 (m, 2F, CF2), ꢀ121,21 (s, 2F, CF2), ꢀ123,52 (s, 2F, CF2),
-123,82 (s, 2F, CF2), ꢀ127,34 (s, 2F, CF2). 13C NMR (100,6 MHz,
CDСl3):
d
¼ 19,38 (CH3), 109,51 (C5), 112.04 (C4,C3), 118.46 (CF3),
130.2 (C9), 137.18 (C8). IR (KBr, , smꢀ1): 1152, 1208, 1243 (CeF),
n
1600, 1515 (C¼Carom), 3017 (CHarom), 2946 (СН3). EIMS, m/z: 410,08
[М] ,
þꢃ, 391,17 [M-F]þꢃ, 167,05 [C3F6eCH3]þꢃ, 148,03 [C3F6eH]þꢃ
3.3.1. Perfluorohexylbenzene (1)
118,05 [C2F4eCH3]þꢃ, 103,11 [C2F4eH]þ, 91,01[C7H7]þꢃ. Found (%): C:
37,92; H: 1,68. C13H7F13. Anal. calc. (%): C, 38.07; H, 1.72; F, 60.21.
The filtrate was concentrated, and the product was isolated in
form of colorless oil. The spectroscopic data for 1 matched the data
reported in the literature [5b].
3.3.4. 1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)-
2-methylbenzene (4)
Table 2
m.p. >300ꢁС. 1Н NMR (400 MHz, CDСl3):
d
¼ 1,96 (s, 3H, CH3),
2,35 (m, 2H,CH2-CF2), 2,61-2,76 (m, 2H, CH2), 7,15e7,30 (m, 3H, Ph),
7,51e7,63 (m,1Н, Ph). IR (KBr,
, smꢀ1): 1157,1206,1241 (CeF),1609,
Yields of product in the cross-coupling reaction of bromobenzene and perfluoro-6-
iodohexane with MX2L catalyst (Scheme 1), room temperature, DMF, undivided cell
with sacrificial anodes (except for Pt anode).
n
1580 (C¼Carom), 3036 (CHarom), 2978 (СН3). EIMS, m/z: 538,08
L
Metal
Anode
Yield,%
þ
[М
]
þꢃ, 519,00 [M-F] ꢃ, 318,97 [C6F13
]
þꢃ, 268,98 [C5F11
]
þꢃ, 218,90
[catalyst: PhBr: С6F13I ]
[C4F9]þꢃ, 168,98 [C3F7]þꢃ, 118,94 [C2F5]þꢃ, 148,08 [C3F6eH]þꢃ, 91,01
[C7H7]þꢃ. Found (%): C, 36.69; H, 1.58. C17H11F17. Anal. calc. (%):C,
37.93; H, 2.06; F, 60.01.
0,01:1:1
0,1:1:1
1:1:1
bpy
bpy
bpy
tpy
bpy
tpy
dbi
bipq
Ni
Zn
Mg
Pt
23
>10
>10
>10
70
57
68
27
28
30
40
81
35
75
77
80
27
34
24
18
19
12
75
71
74
31
31
20
42
84
38
80
78
85
30
37
29
21
20
15
77
71
76
28
30
>10
44
80
37
80
80
74
25
19
3.3.5. 4-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)
benzonitrile (5)
Mg
Cu
Cu
Cu
Cu
Cu
Zn
Zn
Cu
Zn
Cu
Cu
Cu
Cu
Cu
Isolated 1825 g (35%),m.p. > 300ꢁС. 1Н NMR (400 MHz, CDСl3):
d
¼ 1.84e2,05 (m, 2H,CH2-CF2),2.58e2.63 (m, 2H, CH2),7,23 (d, 2H,
3JНН ¼ 15.4 Hz, Ph), 7,63(d, 2H, 3JНН ¼ 15.4 Hz, Ph). IR(KBr,
n
, smꢀ1):
bippdcn
bpy
2251 (dCN), 1146, 1226, 1291 (nC-F), 1603, 1501 (C¼Carom),658, 681,
Co
751, 777, 793, 862,þ885 (С-F). EIMS, m/z:549,01 [M]þꢃ, 529,88 [M-
dtbpy
dtbpy
dmphen
dmphen
bpy
dbi
bipq
bippdcn
F]þꢃ,418,99 [C8F17 ꢃ, 318,91 [C6F13 þꢃ, 268,05 [C5F11 þꢃ, 218,79
] ] ]
[C4F9]þꢃ, 168,91 [C3F7]þꢃ, 118,99 [C2F5]þꢃ. Found (%): C, 37.11; H, 1.42;
N, 2.72, C17H8F17N Anal. calc. (%): C, 37.18; H, 1.47; F, 58.81; N, 2.55.
3.3.6. 4-(perfluorohexyl)benzonitrile (6)
m.p. 215ꢁС. 1Н NMR (400 MHz, CDСl3):
d
¼ 7.68 (d, 2H,

M. Khrizanforov et al. / Journal of Organometallic Chemistry 820 (2016) 82e88
87
3JНН ¼ 10.7 Hz, Ph), 7.75 (d, 3JНН ¼ 10.3 Hz, Ph); 19F NMR(376,5 MHz,
3.4.2. Nickel(II)-2,20:60,200-terpyridine bromide (11)
C6D6):
d
¼ ꢀ81.25 (s, СF3), ꢀ102,1 (m, СF2), ꢀ121.8 (s, СF2), ꢀ122,1
Isolated green-brown powder 6.118 g (88%), NiBr2tpy. 1Н NMR
(s, CF2), ꢀ123,2 (s, CF2), ꢀ126,6 (s, CF2). IR (KBr,
n
, smꢀ1): 2251 (dCN),
(C6D6): 7.1e7.8 (br.m). IR (
n
, smꢀ1): 1580, 1600 (С ¼ С arom). EIMS,
m/z: 450,87 [M]þꢃ, 369,95 [C15H11BrN3Ni]þꢃ, 291,01 [C15H11N3Ni]þ
.
ꢃ
1146, 1226, 1291 (nC-F), 1603, 1501 (C¼Carom),658, 681, 751, 777, 793,
862, 8þ85 (С-F); EIMS, m/z: 420,8 [M]þꢃ, 401,0 [M-F]þþꢃ, 318,95
Found (%): (%): C: 39,58; H: 2,38; N: 9,25. C15H11Br2N3Ni. Anal. calc.
(%): C: 39,88; H: 2,45; Br: 35,37; N: 9,30.
[C6F13] ]
ꢃ, 268,00 [C5F11 þꢃ, 218,76[C4F9]þꢃ, 168,95 [C3F7] ꢃ, 118,90
[C2F5]þꢃ. Found (%): C: 36,98; H: 0,91; N: 3,31. C13H4F13N. Anal. calc.
(%): C: 37,07; H: 0,96; F: 58,64; N: 3,33.
3.4.3. Nickel(II)-(4,40-di(tert-butyl-2,20-bipyridine) bromide (12)
Isolated green powder 7.039 g (79%), NiBr2dtbpy. 1Н NMR
(400 MHz, CDCl3):
d
¼ 1.43 (br.s., 18Н, t-Bu), 7.12e7.79 (m, 6Н, Py).
3.3.7. 3-(perfluorohexyl)pyridine (7)
IR (KBr, n
, smꢀ1): 1603, 1597 (arom. of het.); 3073 (CH3), 870 (dСН);
b.p. 210ꢁС. 1Н NMR (400 MHz, CDСl3):
d
¼ 8.80 (d, Pу, JНН ¼ 5.6),
8.88 (s, 2H, Py), 7.39 (dd, JНН ¼ 6.4, 2,1 Hz, H), 7.89 (d, JНН ¼ 5.9 Hz).
19F NMR (376,5 MHz, C6D6):
¼ ꢀ81.40 (s, CF3), ꢀ111,70 (m,
СF2), ꢀ121.4 (s, СF2), ꢀ121,9 (s, СF2), ꢀ122,8 (s, СF2), ꢀ126,3 (s, CF2).
IR (KBr,
, smꢀ1): 1150, 1241, 1279, 1350 (CeF), 1667 (C]N), 1605-
EIMS, m/z: 485,96 [M]þ
,
405,05 [C18H24BrN2Ni]þ
, 326,13
ꢃ
ꢃ
[C18H24N2Ni]þ
.
Found (%): C: 45,03; H: 5,06; N: 5,71.
ꢃ
d
C18H24Br2N2Ni. Anal. calc. (%):C: 44,40; H: 4,97; Br: 32,82; Ni:
12,05; N: 5,75.
n
149þ3 (Py), 654, 683, 752, 777, 794, 864,þ886 (
[C4F9]þꢃ, 168,98 [C3F7]þꢃ, 118,94 [C2F5]þꢃ. Found (%): C: 33,11; H:
0,99; N: 3,49. C11H4F13N. Anal. calc. (%): C: 33,27; H: 1,02; F: 62,19;
N: 3,53.
d
Rf). EIMS, m/z: 397,01
3.4.4. Nickel(II)-2,9-dimethyl-1 10-phenanthroline bromide (13)
[М] ] ]
ꢃ, 376,14 [M-F]þꢃ, 318,97 [C6F13 ꢃ, 268,98 [C5F11 þꢃ, 218,90
Isolated green powder 5,321 g (59%),NiBr2dmphen; IR (KBr,
n
m/z:
,smꢀ1): 1595, 1585 (arom. het.), 3065 (СНhet), 864, 877 (dСН).EIMS,
ꢃ
ꢃ
425,87
[M]þ
,
346,95
[C14H12BrN2Ni]þ
,
266,04
[C14H12N2Ni]þꢃ; Found (%): (%):С: 39,32; H: 2,54; N: 6,63; M: 14,01.
C
14H12Br2N2Ni. Anal. calc. (%):C: 39,40; H: 2,83; Br: 37,45; N: 6,56;
3.3.8. 2-(perfluorohexyl)pyridine (8)
Ni: 13,75.
1Н NMR (400 MHz, CDСl3):
d
¼ 7.91 (d, Py, JНН ¼ 7.8), 8.12 (t, Py,
3JНН ¼ 7.2), 7.41 (dd, Py JНН 5.1, 1.1), 7.88 (d, Py JНН ¼ 9.8).19
F
3.4.5. Nickel(II)-1,2-Bis(diphenylphosphino)ethane bromide (14)
NMR(376,5 MHz, C6D6): ꢀ81.40 (s, CF3), ꢀ104,1 (m, СF2), ꢀ122.1 (m,
Isolated green powedr 6,999 g (62%) NiBr2dppe; EIMS, m/z:
615,91 [M]þꢃ, 534,99 [C26H24BrNiP2]þꢃ, 456,07 [C26H24NiP2]þ
Found (%): (%):C: 50,54; H: 3,85;
(%): C: 50,62; H: 3,92; Br: 25,90; Ni: 9,51; P: 10,04.
;
ꢃ
СF2), ꢀ122,8 (s, СF2), ꢀ123,4 (s, СF2), ꢀ126,9 (s, СF2). IR (KBr,
n,
smꢀ1): 1150, 1241, 1279, 1350 (CeF), 1665 (C¼Npyridine), 651, 684,
М: 9,57. C26H24Br2NiP2 Anal. calc.
753, 778, 799, 864, 888 (C-F). EIMS, m/z: 397,01 [М]
þꢃ, 376,14 [M-
F]þꢃ, 318,97 [C6F13
[C3F7]þꢃ, 118,94 [C2F5]þꢃ. Found (%): C: 33,11; H:0,99; N: 3,49.
11H4F13N. Anal. calc. (%):C: 33,27; H: 1,02; F: 62,19; N: 3,53.
] , 268,98 [C5F11]
þꢃ, 218,90[C4F9]þꢃ, 168,98
þꢃ
3.4.6. Cobalt(II)-2,9-dimethyl-1 10-phenanthroline chloride (15)
C
Isolated bright blue powder (79%) CoCl2dmphen; IR (KBr,
n,
smꢀ1): 1591, 1567, (arom.); 3065 (nСН); 864 (dСН).EIMS, m/z: 336,97
[M]þ
,
338,97 (64,0%), 302,0021 [C14H12ClCoN2]þ
,
263,0337
ꢃ
ꢃ
3.3.9. 3-(perfluorohexyl)furan (9)
[C14H12CoN2]þ
. Found (%): (%):C: 49,53; H: 3,56; N: 8,31.
ꢃ
b.p. 176ꢁС. 1Н NMR (400 MHz, CDСl3):
d
¼ 6.44 (d, 1Н,
3JHH ¼ 3.4 Hz, RfeC]CH), 6.81 (dd, 1Н, JHH ¼ 3.4, 1.8 Hz,
3
C14H12Cl2CoN2. Anal. calc. (%):C: 49,73; H: 3,58; Cl: 20,97; Co: 17,43;
3
ОСН ¼ СН), 7.49 (d, 1Н, JHH ¼ 1.8 Hz, OCH). 19F NMR (376,5 MHz,
N: 8,29.
C6D6):
d
¼ ꢀ81.50 (s, 3F, CF3), ꢀ111,4 (br. S., 2F, СF2), ꢀ122.0 (br.s., 2F,
CF2), ꢀ122,9 (s, 4F, СF2), ꢀ126,4 (s, 2F, CF2). IR (KBr,
n
, smꢀ1): 1132,
3.4.7. Cobalt(II)-2,2'-bipyridine chloride (16)
Isolated dark blue powder 4.763 g (91%) CoCl2bpy. 1Н NMR
1221, 1284, 1341 (CeF), 1603, 1500, 1346 (C-Ofuran), 1086 (CO-Cst),
, smꢀ1): 1601, 1581 (arom.); 3102
þꢃ
(C6D6): 7.10e7.72 (br.m). IR (KBr,
n
654, 683, 759, 772, 791, 864, 886 (dRf). EIMS, m/z: 386,01 [
М]
,
,
nСН); 783 (dСН); EIMS,m/z: 284,94 [M]þꢃ, 249,97 [C10H8ClN2Co]þ
,
ꢃ
375,17 [M-F]þꢃ, 318,95 [C6F13 þꢃ, 268,00 [C5F11
]
]
þꢃ, 218,76[C4F9]þꢃ
(
215,00 [C10H8N2Co]þꢃ; Found (%): (%):C: 41,88; H: 2,78;
М
: 20,54; N:
168,95 [C3F7]þꢃ, 118,90 [C2F5]þꢃ. Found (%): C: 31,01; H: 0,75.
9,83. C10H8Cl2N2Co. Anal. calc. (%):C: 41,99; H: 2,82; Cl: 24,79; Co:
20,60; N: 9,79.
C
10H3F13O. Anal. calc. (%):C: 31,11; H: 0,78; F: 63,97; O: 4,14.
3.4. Preparation of complexes (general procedure)
3.4.8. Cobalt(II)-(4,4'-di(tert-butyl-2,2'-bipyridine) chloride (17)
Isolated dark aquamarine powder 7.765 g (78%) CoCl2dtbpy. 1Н
18.3 mmol of hexahydrate CoCl2 or trihydrate NiBr2 was entirely
dissolved in 100 ml of ethanol and then a solution of 18,3 mmol of
the ligand in 100 ml of ethanol was added dropwise (during
approximately 10 min) to the stirred solution of metal salt at room
temperature. After adding of entire ligand/ethanol solution, the
stirring proceeded during 24 h. After that, the precipitate was
filtered and washed first with two 40 ml portions of glacial ethanol
and then with one 20 ml portion of diethyl ether. Drying of the
precipitate under vacuum (ꢀ10 torr) at room temperature
(t ¼ 23 ꢁC) resulted in a powder.
NMR (C6D6):
d
¼ 1.42 (br.s, 18 Н,СН3), 7.13e7.78 (br.m). ESI m/z:
397,06 [C18H24Cl2CoN2]þ
,
296,94 [C18H24ClCoN2]þ
,
263,97
ꢃ
ꢃ
[C18H24CoN2]þꢃ. Found (%): (%):C: 54,17; H, 6.00; Hal: 17,81; M:
14,64; N, 7.11.C18H24Cl2CoN2. Anal. calc. (%):C, 54.29; H, 6.07; Cl,
17.81; Co, 14.80; N, 7.03.
3.4.9. Nickel(II)e1H,10H-2,2'-bibenzo[d]imidazole bromide (18)
Isolated yellow-red powder 4.0598 g (49%) NiBr2dbi. EIMS, m/z:
451,86 [C14H10Br2N4Ni]þ
,
372,94 [C14H10BrN4Ni]þ
,
292,03
ꢃ
ꢃ
[C14H10N4Ni
]
þꢃ; Found (%): (%):C: 37,03; H: 2,01; Hal: 34,91; N:
4
12,42.C14H10Br2N4Ni Anal. calc. (%):C: 37,14; H: 2,23; Br: 35,30; N:
12,37; Ni: 12,96.
3.4.1. Nickel(II)-2,20-bipyridine bromide (10)
Isolated light green powder 6.255 g (91%) NiBr2bpy. 1Н NMR
(C6D6,
d
, J/Hz): 7.2e7.9 (br.m). IR (KBr,
n
, smꢀ1): 1599, 1584 (arom.),
3.4.10. Cobalt(II)e1H,10H-2,20-bibenzo[d]imidazole chloride (19)
3105 (СНhet); EIMS, m/z: 373,92 [
М]
þꢃ. Found (%): C: 32,06; H: 2,15;
Isolated green powder 3.576 g (53%) CoCl2dbi. EIMS, m/z: 366,96
ꢃ
N: 7,48. C10H8Br2N2Ni. Anal. calc. (%):C: 32,23; H: 2,24; Br: 42,31; N:
[C14H10Cl2CoN4]þꢃ, 331,99 [C14H10ClCoN4]þꢃ, 297,02 [C14H10CoN4]þ
.
7,57.
Found (%): C: 45,44; H: 2,54; N: 15,13. Hal: 19,29.C14H10Cl2CoN4.

88
M. Khrizanforov et al. / Journal of Organometallic Chemistry 820 (2016) 82e88
b) K. Sato, A. Tarui, M. Omote, A. Ando, I. Kumadaki, Synthesis 2010 (2010)
1865e1882;
Anal. calc. (%):C: 45,61; H: 2,73; Cl: 19,23; Co: 17,23; N: 15,20.
c) J.A. Ma, D. Cahard, Chem. Rev. 108 (2008) 1e43;
d) V. Soloshonok, Fluorine-containing synthons, in: ACS Symposium Series
911, American Chemical Society, Washington, DC, 2005;
e) B. Lantano, M.R. Torviso, S.M. Bonesi, S. Barata-Vallejo, A. Postigo, Coord.
Chem. Rev. 285 (2015) 76e108;
3.4.11. Nickel(II)-2-(1H-benzo[d]imidazol-2-yl)-3-
phenylquinoxaline bromide (20)
~
Isolated yellow powder 4.85 g (49%) NiBr2bipq. EIMS, m/z:
539,89 [M]þꢃ, 460,97 [C21H14Br2NiN4]þꢃ, 380,06 [C21H14Br2NiN4]þ
.
ꢃ
f) D.Y. Mikhaylov, Y.H. Budnikova, Russ. Chem. Rev. 82 (2013) 835e864.
[3] a) Y. Kobayashi, I. Kumadaki, S. Sato, N. Hara, E. Chikami, Chem. Pharm. Bull.
18 (1970) 2334e2339;
Found (%): C: 46,58; H: 2,53; N: 10,31; Hal: 29,35, C21H14Br2NiN4
Anal. calc. (%): C: 46,63; H: 2,61; Br: 29,55; N: 10,36; Ni: 10,85.
b) J.M. Paratian, S. Sibille, J. Perichon, J. Chem. Soc. Chem. Commun. 1 (1992)
53e54;
3.4.12. Cobalt(II)-2-(1H-benzo[d]imidazol-2-yl)-3-
phenylquinoxaline chloride (21)
c) Y. Kobayashi, K. Yamamoto, I. Kumadaki, Terahedron. Lett. 20 (1979)
4071e4072;
d) T. Kitazume, S. Nakajima, J. Fluor. Chem. 125 (2004) 1447e1449;
e) F. Cottet, M. Schlosser, Eur. J. Org. Chem. 2 (2002) 327e330;
f) J. Kim, J. Shreeve, Org. Biomol. Chem. 2 (2004) 2728e2734;
g) S. Lectard, Y. Hamashima, M. Sodeoka, Adv. Synth. Catal. 352 (2010)
2708e2732;
Isolated khaki powder 4.220 g (51%) CoCl2bipq. EIMS, m/z:
450,99 [M]þꢃ, 416,02 [C21H14ClCoN4]þꢃ, 381,29 [C21H14CoN4]þ
;
ꢃ
Found (%): C: 55,57; H: 3,03; N: 12,31. C21H14Cl2CoN4. Anal. calc. (%):
C: 55,78; H: 3,12; Cl: 15,68; Co: 13,03; N: 12,39.
h) H. Kawai, A. Kusuda, S. Nakamura, M. Shiro, N. Shibata, Angew. Chem. Int.
Ed. 48 (2009) 6324e6327;
i) G.K.S. Prakash, S. Chacko, S. Alconcel, T. Stewart, T. Mathew, G.A. Olah,
Angew. Chem. Int. Ed. 46 (2007) 4933e4936.
3.4.13. Nickel(II)-5-(1H-benzo[d]imidazol-2-yl)-6-phenylpyrazine-
2,3-dicarbonitrile bromide (22)
[4] a) M. Khrizanforov, S. Strekalova, V. Khrizanforova, V. Grinenko, K. Kholin,
M. Kadirov, T. Burganov, A. Gubaidullin, T. Gryaznova, O. Sinyashin, L. Xu,
D.A. Vicic, Y. Budnikova, Dalton Trans. 44 (2015) 19674e19681;
b) G.G. Dubinina, W.W. Brennessel, J.L. Miller, D.A. Vicic, Organometallics 27
(2008) 3933e3938;
Isolated yellow-green powder 4.849 g (49%) NiBr2bippdcn.
EIMS, m/z: 539,87 [M]þ
,
416,00 [C19H10BrN6Ni]þ
,
381,03
[C19H10N6Ni]þꢃ. Found (%): C: 42,08; H: 1,81; N: 15,50; Hal: 29,49;
19H10Br2N6Ni Anal. calc. (%): C: 42,20; H: 1,86; Br: 29,55; N: 15,54;
ꢃ
ꢃ
C
c) H. Morimoto, T. Tsubogo, N.D. Litvinas, J.F. Hartwig, Angew. Chem. 123
(2011) 3877e3882;
d) E.J. Cho, T.D. Senecal, T. Kinzel, Y. Zhang, D.A. Watson, S.L. Buchwald, Sci-
ence 328 (2010) 1679e1681.
Ni: 10,85.
3.4.14. Cobalt(II)-5-(1H-benzo[d]imidazol-2-yl)-6-phenylpyrazine-
2,3-dicarbonitrile chloride (23)
[5] a) Y.B. Dudkina, M.N. Khrizanforov, T.V. Gryaznova, Y.H. Budnikova,
J. Organomet. Chem. 751 (2014) 301e305;
b) M. Khrizanforov, T. Gryaznova, O. Sinyashin, Y. Budnikova, J. Organomet.
Chem. 718 (2012) 101e104;
Isolated dark green powder 4.054 g (49%) CoCl2bippdcn. EIMS,
m/z: 450,97 [M]þꢃ, 416,00 [C19H10ClN6Сo]þꢃ, 381,03 [C19H10N6Co]þ
.
ꢃ
c) D.Y. Mikhaylov, Y.H. Budnikova, T.V. Gryaznova, Y.B. Dudkina,
M.N. Khrizanphorov, O. Kataeva, D.A. Vicic, Dalton Trans. 4 (2012) 165e172;
d) Y.B. Dudkina, T.V. Gryaznova, Y.N. Osin, V.V. Salnikov, N.A. Davydov,
S.V. Fedorenko, A.R. Mustafina, D.A. Vicic, O.G. Sinyashin, Y.H. Budnikova,
Dalton Trans. 44 (2015) 8833e8838;
Found (%): C: 50,29; H: 2,18. C19H10Cl2N6Co. Anal. calc. (%): C: 50,47;
H: 2,23; Cl: 15,68; Co: 13,03; N: 18,59.
Acknowledgment
e) M.N. Khrizanforov, T.V. Gryaznova, D.Y. Mikhailov, Y.H. Budnikova,
O.G. Sinyashin, Russ. Chem. Bull. 61 (2012) 1560e1563;
f) Y.B. Dudkina, D.Y. Mikhailov, T.V. Gryaznova, S.G. Fattakhov, Y.G. Budnikova,
O.G. Sinyashin, Russ. Chem. Bull. Int. Ed. 62 (2013) 2362e2366;
g) Y.B. Dudkina, D.Y. Mikhaylov, T.V. Gryaznova, A.I. Tufatullin, O.N. Kataeva,
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This work was supported by the RFBR grants 14-03-31423-
mol_a.
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