Triarylantimony(V) catecholates – Derivatives of 4,5-difluoro-3,6-di-tert-butyl-o-benzoquinone

Article abstract of DOI:10.1016/j.jorganchem.2016.09.021

New triarylantimony(V) 4,5-difluoro-3,6-di-tert-butylcatecholates of (4,5-F₂-3,6-Cat)SbAr₃type, where Ar is p-fluorophenyl (1), p-chlorophenyl (2), phenyl (3), have been synthesized and characterized in details. The electrochemical p

Full text of DOI:10.1016/j.jorganchem.2016.09.021

Accepted Manuscript
Triarylantimony(V) catecholates – Derivatives of 4,5-difluoro-3,6-di-tert-butyl-o-
benzoquinone
Andrey I. Poddel'sky, Ivan V. Smolyaninov, Georgy K. Fukin, Nadezhda T. Berberova,
Vladimir K. Cherkasov, Gleb A. Abakumov
PII:
S0022-328X(16)30427-2
10.1016/j.jorganchem.2016.09.021
JOM 19633
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 22 June 2016
Revised Date: 9 September 2016
Accepted Date: 22 September 2016
Please cite this article as: A.I. Poddel'sky, I.V. Smolyaninov, G.K. Fukin, N.T. Berberova, V.K.
Cherkasov, G.A. Abakumov, Triarylantimony(V) catecholates – Derivatives of 4,5-difluoro-3,6-
di-tert-butyl-o-benzoquinone, Journal of Organometallic Chemistry (2016), doi: 10.1016/
j.jorganchem.2016.09.021.
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ACCEPTED MANUSCRIPT

Triarylantimony(V) catecholates – derivatives of 4,5-difluoro-3,6-di-tert-butyl-o-
ACCEPTED MANUSCRIPT
benzoquinone
a,*
b
a
Andrey I. Poddel’sky , Ivan V. Smolyaninov , Georgy K. Fukin , Nadezhda T.
c
a
a
Berberova , Vladimir K. Cherkasov , Gleb A. Abakumov
a
G.A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences. 603950,
Russia, Nizhny Novgorod, 49 Tropinina str. e-mail: aip@iomc.ras.ru
b
Southern Scientific Centre of Russian Academy of Sciences, 344006, Russia, Rostov-on-Don, 41
Chekhova str.
c
Astrakhan State Technical University, 414025, Russia, Astrakhan’, 16 Tatisheva str.
Abstract
New triarylantimony(V) 4,5-difluoro-3,6-di-tert-butylcatecholates of (4,5-F -3,6-Cat)SbAr3 type,
2
where Ar is p-fluorophenyl (1), p-chlorophenyl (2), phenyl (3), have been synthesized and
characterized in details. The electrochemical properties of complexes 1-3 were investigated by means
of cyclic voltammetry in comparison with the redox properties of related triarylantimony(V) 4-chloro-
3
,6-di-tert-butylcatecholates (4-Cl-3,6-Cat)SbAr (complexes 4-6). The electrochemical oxidation of
3
+
complexes proceeds as two successive one-electron steps leading to monocations of [(SQ)SbAr ] type
3
2+
and dications [(Q)SbAr ] . The presence of two fluorine substituents in redox-active ligand in 1-3
3
leads to the increase of the stability of monocationic derivatives. The molecular structures of (4,5-F2-
3
,6-Cat)SbPh (3) and related 4-chlorosubstituted catecholato (4-Cl-3,6-Cat)SbPh (6) in crystal were
3 3
determined by single-crystal X-ray analysis. In crystal form, catecholates 3 and 6 form hexamolecular
cycles (CatSbPh ) due to the intermolecular Hphenyl…Sb interactions.
3
6
Keywords: redox active ligand, catecholate, antimony(V), NMR, X-ray, cyclic voltammetry.
1

1
. Introduction
ACCEPTED MANUSCRIPT
The interest to antimony(V) complexes bearing redox-active ligands of o-
quinonato type is caused by the intriguing variety of structural forms found for these
compounds [1,2] as well as interesting chemical and biochemical properties [3,4].
Triphenylantimony(V) o-amidophenolato (AP) and some catecholato (Cat) complexes
demonstrate ability of reversible molecular oxygen binding in mild conditions with a
formation of spiroendoperoxides [3c,5]. The nature of functional groups – substituents
at the redox active ligand as well as at the central antimony atom was shown to
influence the redox properties of catecholates: electron-donor substituents facilitate the
one electron oxidation of Cat ligand while electron-withdrawing groups shift the
oxidation potential of Cat ligand to the anodic region [6,7]. From the viewpoint of
interaction with molecular oxygen, the electron-donor substituents in Cat ligand
promote the formation of dioxygen-bound compounds (spiroendoperoxides) and, on the
contrary, electron-withdrawing groups in Cat ligand impede the reaction of the
corresponding catecholates with molecular oxygen [6b,8]. The combination of electron-
acceptor groups both in redox active Cat ligand and in the aryl substituents at antimony
should give an interesting effect on the redox properties of such catecholates. In the
present work we report on the spectral and structural characterization of
triarylantimony(V) 4,5-difluoro-3,6-di-tert-butyl-catecholates (where aryl is p-
fluorophenyl, p-chlorophenyl, phenyl), and investigation of their electrochemical
properties in comparison with the related triarylantimony(V) 4-chloro-3,6-di-tert-butyl-
catecholates.
2

2
. Results and discussion
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2
.1. Synthesis and characterization
Triarylantimony(V) catecholates (4,5-F -3,6-Cat)Sb(p-F-Ph) (1), (4,5-F -3,6-
2
3
2
Cat)Sb(p-Cl-Ph) (2), (4,5-F -3,6-Cat)SbPh (3) (Scheme 1) were synthesized by the
3
2
3
oxidative addition of 4,5-difluoro-3,6-di-tert-butyl-o-benzoquinone to corresponding
triarylstibines. The related triarylantimony(V) catecholates (4-Cl-3,6-Cat)Sb(p-F-Ph)3
(
4), (4-Cl-3,6-Cat)Sb(p-Cl-Ph) (5) and (4-Cl-3,6-Cat)SbPh (6) were synthesized as
3
3
described earlier [6d].
But
But
O
O
O
O
F
F
SbR3
SbR3
Cl
But
But
(
(
(
4,5-F -3,6-Cat)Sb(p-F-Ph)3
1
(4-Cl-3,6-Cat)Sb(p-F-Ph)3
(4-Cl-3,6-Cat)Sb(p-Cl-Ph)3
(4-Cl-3,6-Cat)SbPh3
4
5
6
2
4,5-F -3,6-Cat)Sb(p-Cl-Ph) 2
2
3
4,5-F -3,6-Cat)SbPh3
3
2
Scheme 1
1
13
19
Complexes 1-3 were characterized by means of IR-, H, C and F NMR
spectroscopy, elemental analysis. The IR and NMR spectral data (see Supplementary
material) confirm the proposed composition of complexes.
1
3
The C NMR spectra of antimony(V) catecholates 1-3 containing fluorine atoms
th
th
in 4 and 5 positions of Cat ligand are complicated due to the presence of coupling
1
3
interactions of carbon nuclei with fluorines. For example, the C NMR spectrum of
(
4,5-F -3,6-Cat)Sb(p-F-Ph) (1) in the aromatic region is shown on Figure 1. The
2
3
carbon nuclei of catecholato ligand responsible for the observable multiplets in the
2
aromatic region: a doublet of doublets at δ=120.21 ppm with J(C,F) = 7.1 Hz and
3
t
3
J(C,F) = 3.2 Hz from carbon atoms C(Bu ), a triplet at δ=140.29 ppm with J(C,F) ≈
3

4
J(C,F) = 6.1 Hz from carbons of C-O groups, and a doublet of doublets at δ=143.64
ACCEPTED MANUSCRIPT
1
2
th
th
ppm with J(C,F) = 237.9 Hz and J(C,F) = 18.2 Hz from carbons in 4 and 5
positions of aromatic ring bound with fluorines. The carbons of p-fluorophenyl
2
4
substituents give rise to doublets at δ = 116.82 ( J(C,F)=20.9 Hz), 132.19 ( J(C,F)=3.9
3
1
Hz), 136.79 ( J(C,F)=8.1 Hz) and 164.84 ( J(C,F)=252.9 Hz) ppm.
1
3
Figure 1. The aromatic region of C NMR spectrum of complex (4,5-F -3,6-Cat)Sb(p-
2
F-Ph) (1) (CDCl , 200 MHz, RT).
3
3
19
The F NMR spectra of (4,5-F -3,6-Cat)Sb(p-Cl-Ph) (2) and (4,5-F -3,6-
2
3
2
Cat)SbPh (3) contain one signal at -149.13 ppm and -150.22 ppm, respectively, while
3
1
9
F NMR spectrum of (4,5-F -3,6-Cat)Sb(p-F-Ph) (1) reveals two singlets at -149.38
2
3
ppm and -106.96 ppm due to the presence of two types of fluorine nuclei.
2
.2. Crystal structures
The molecular structures of (4,5-F -3,6-Cat)SbPh3 (3) and related
2
triphenylantimony(V) 4-chloro-3,6-di-tert-butylcatecholate, (4-Cl-3,6-Cat)SbPh (6), in
3
4

crystals were determined by single-crystal X-ray analysis (Figure 2). The X-ray quality
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crystals of both complexes were grown from the solution of n-hexane. The selected
bond lengths and angles are listed in Table 1.
{Please, insert Table 1 here}
Figure 2. Molecular structures of (4,5-F -3,6-Cat)SbPh (3) (top) and (4-Cl-3,6-
2
3
Cat)SbPh (6) (bottom) in crystals with the thermal ellipsoids of 30% probability. The
3
hydrogen atoms are omitted for clarity.
The central antimony atoms Sb(1) in both complexes adopt the distorted tetragonal
pyramidal environment. The base of pyramid is formed by oxygen atoms O(1), O(2) of
chelating ligand and carbon atoms C(15) and C(21) of phenyl groups. The bond angles
5

O(1)-Sb(1)-C(21) and O(2)-Sb(1)-C(15) are equal to 142.10(9) and 155.87(10)º for 3,
ACCEPTED MANUSCRIPT
1
54.97(8) and 143.68(7)º for 6 respectively. At the same time bond angles between
equatorial atoms and apical carbon atom C(27) lie in the range of 97.53(10) -
09.20(11)º for 3 and 98.43(7)-108.45(8)º for 6. In the accordance with a model
describing pentacoordinated compounds [9] we may apply the geometrical parameter τ
(β-α)/60 where α and β – bond angles in the pyramid base and β is a biggest angle: in
1
=
the ideal tetragonal pyramid τ=0 (because β=α), while τ=1 (β=180º, α=120º) in ideal
trigonal bipyramid. This parameter τ=0.23 for 3 and 0.19 for 6. Consequently, the
deviation of geometries from the ideal tetragonal pyramid is 23 and 19 % respectively.
The equatorial bond distances Sb(1)-C(15) and Sb(1)-C(21) in 3 are 2.143(3) and
2
.136(3) Å, respectively, while the apical bond C(27) is shorter by 0.03-0.04 Å.
The geometrical characteristics of redox active ligands correspond to catecholato
form of ligand. The bonds O(1)-C(1) and O(2)-C(2) (1.358(3) and 1.357(4) Å,
respectively) fall in the range typical for ordinary O-C bonds in different catecholates
[1b-g,3c,6d].
The complex molecules form 2D structure with channels (Fig. 3a). The channels
in crystal cell of 3 are fulfilled with guest n-hexane molecules in the ratio “n-hexane :
complex 3” as 1 : 6.
In crystal the intermolecular interactions Sb…H are observed (Fig. 3b), and they
lead to the formation of 36-atomic macrocycle [(4,5-F -3,6-Cat)SbPh ] consisting of
2
3 6
six molecules of antimony(V) catecholate. The contacts H(24)…Sb(1) are equal to
.306(3) Å in 3 and 3.291(3) Å in 6 that is close to the sum of Van-der-Vaals radii of
3
the atoms Sb and H (3.4 Å, [10a]; 3.2 Å [10b]) and a “formal” coordination number of
6

the central antimony atom increases to 6. The same situation was observed in the case
ACCEPTED MANUSCRIPT
of triphenylantimony(V) 4-nitro-substituted 3,6-di-tert-butylcatecholate [11].
Figure 3. The crystal cell of (4,5-F -3,6-Cat)SbPh (3) (top) and the hexamolecular
2
3
macrocycle [(4,5-F -3,6-Cat)SbPh ] (bottom).
2
3 6
7

2
.3. Electrochemical investigations
ACCEPTED MANUSCRIPT
The electrochemical properties of antimony(V) compounds have been investigated by
cyclic voltammetry (CV). The values of the redox potentials of complexes 1-6 and
catecholates (3,6-Cat)Sb(p-FPh) (7), (3,6-Cat)SbPh (8) are shown in Table 2.
3
3
{Please, insert Table 2 here}
The electrochemical oxidations of complexes 1-3 in dichloromethane proceed as two
successive stages leading to the formation of mono- and dicationic forms ([(4,5-F -3,6-
2
+
2+
SQ)SbAr ] ) and ([(4,5-F -3,6-Q)SbAr ] ), respectively (Scheme 2). At the potential
3
2
3
switch to + 1.20 V on CV curve, the quasireversible (I /I = 0.92-0.97) one electron
с
а
oxidation peak was observed (Figure 4(1)) reflecting the formation of relatively stable
+
cationic form [(4,5-F -3,6-SQ)SbAr ] containing o-semiquinone radical.
2
3
tBu
tBu
tBu
E1
E2
p
2+
1
/2
F
F
O
O
F
F
O
O
F
F
O
O
-
e-
- e-
+ e-
V
V
V
Sb Ar3
e-
Sb Ar
Sb Ar
3
3
+
tBu
tBu
tBu
+
2+
(
4,5-F -3,6-Cat)SbAr3
[(4,5-F -3,6-SQ)SbAr ]
[(4,5-F -3,6-Q)SbAr ]
2 3
2
2
3
Scheme 2
th
th
The insertion of electron withdrawing fluorine atoms to the 4 and 5 positions of
catecholato ligand increases the stability of the o-semiquinonato form (4,5-F -3,6-SQ)
2
of redox-active ligand formed during the oxidation as compared with previously studied
antimony(V) 4-chloro-3,6-di-tert-butylcatecholates 4-6 [6a,d]. On the reverse scan of
CV in cathodic region (Figure 4(1)) the reduction peak of 4,5-di-fluoro-3,6-di-tert-
butyl-o-benzoquinone, 4,5-F -3,6-Q, was observed due to a chemical reaction in a
2
8

solvent volume - partial decoordination of o-semiquinone radicals which
ACCEPTED MANUSCRIPT
disproportionate rapidly to the corresponding o-benzoquinone and catecholate.
Figure 4. The CV curve of (4,5-F -3,6-Cat)Sb(p-F-Ph) (1): 1 – the potential switch
2
3
from -0.70 to +1.20 V; 2 – the potential switch from -0.70 to +1.70 V (CH Cl , GC
2
2
-3
-1
electrode, C = 2ꢀ10 M, 0.1 М NBu ClO , V = 0.2 Vꢀs , vs. Ag/AgCl/KCl(sat.)).
4
4
The second oxidation peak for complexes 1-3 is shifted to the cathodic region in
comparison with earlier studied antimony(V) catecholates (Table 2) and observed in the
2
+
potential range of 1.34-1.39 V. The dicationic derivatives of [(Q)SbAr ] type are
3
unstable and decompose in solution with liberation of free o-benzoquinone and the
intensity of its reduction peak increases upon the potential switching to 1.6-1.8 V.
The comparison of electrochemical behavior of tris-p-fluorophenylantimony(V)
catecholates (4,5-F-3,6-Cat)Sb(p-F-Ph) (1), (4-Cl-3,6-Cat)Sb(p-F-Ph) (4) and (3,6-
3
3
Cat)Sb(p-F-Ph) (7) allows to conclude that the potential of transition “catecholate/o-
3
semiquinonate” is more pronouncedly shifted to the anode region by the presence of
chlorine atom in catecholato ligand (complex 4) rather than the presence of two fluorine
9

1
atoms (complex 1). Moreover, the difference between the first oxidation potentials E
1
/2
ACCEPTED MANUSCRIPT
of (4,5-F-3,6-Cat)SbPh (3) and (3,6-Cat)SbPh (8) is only 0.01 V while the second
3
3
2
oxidation stage proceeds for complex 3 is even easier than that one for complex 8 (Е
p
=
1.36 V and 1.40 V, respectively). The same situation is observed for complexes (4,5-
1
F-3,6-Cat)Sb(p-F-Ph) (1) and (3,6-Cat)Sb(p-F-Ph) (7): E
= 0.92 V versus 0.90 V
3
3
1/2
2
p
and Е = 1.34 V versus 1.40 V, respectively. Such observations allos us to conclude
that fluorine substituents in catecholato ligand behave rather as only weak electron
acceptors if not as weak electron-donors that can be explained in the therms of inductive
and mesomeric effects. The highest occupied molecular orbital of Cat ligand is a π-MO
and 2p-orbitals of fluorines allow an effective overlap with π-system of catecholato
ring, and the positive mesomeric effect of fluorine atoms prevails on their negative
(electron-withdrawing) inductive effect.
3
. Conclusions
Thus, three new 4,5-difluoro-3,6-di-tert-butylcatecholates of triarylantimony(V) have
been synthesized and characterized. The electrochemical oxidation of complexes 1-3
proceeds on the redox-active ligand with a consecutive formation of mono- and
dicationic derivatives. In contrast to the earlier investigated antimony(V) catecholates
[7a,b], 4,5-difluoro-3,6-di-tert-butylcatecholates 1-3 demonstrate the increase of the
stability of electrogenerated monocationic forms and only a weak influence of fluorine
atoms in redox active ligand on the shift of the first oxidation potential (Cat/SQ) to the
anodic region; at the same time the second oxidation step (SQ/Q) for complexes is even
easier than that for the corresponding triarylantimony(V) 3,6-di-tert-butylcatecholates
1
0

implying the predominance of positive mesomeric effect of fluorine atoms in 4,5-
ACCEPTED MANUSCRIPT
difluoro-3,6-di-tert-butylcatecholates. In the accordance with X-ray data, complexes
(
4,5-F -3,6-Cat)SbPh and (4-Cl-3,6-Cat)Sbh adopt distorted tetragonal pyramidal
2
3
3
geometry.
4
. Experimental part
4
.1. General considerations
All the experiments on the synthesis and study of properties of complexes were
carried out in evacuated ampoules in the absence of oxygen and water. In all cases the
yield was more 90%. The solvents used were purified and dehydrated by standard
methods [12]. Triarylstibines were synthesized in the accordance with the described
procedures [13]. 4,5-Difluoro-3,6-di-tert-butyl-o-benzoquinone was obtained in the
laboratory of chemistry of organoelemental compounds of IOMC RAS as described in
ref. [14]. The synthesis and spectroscopic characteristics of catecholates (4-Cl-3,6-
Cat)Sb(p-F-Ph) (4), (4-Cl-3,6-Cat)Sb(p-Cl-Ph) (5), (4-Cl-3,6-Cat)SbPh (6) based on
3
3
3
4
-chloro-3,6-di-tert-butyl-o-benzoquinone were described in ref. [6a,d].
-1
The infrared spectra of the complexes in the 4000–400 cm range were recorded
1
13
19
on a FSM 1201 Fourier-IR spectrometer in nujol. The H, C and F NMR spectra
were recorded in CDCl solution using Fourier-NMR spectrometer “Bruker Avance
3
1
13
III”, with Me Si as internal standard for H and C NMR measurements and CFCl as a
4
3
19
standard for F NMR measurements. The C, H, N elemental analysis was performed on
an Elemental Analyzer Euro EA 3000 instrument; the Fe, Sb, Sn, Cl and Br contents
were accomplished by combustion analysis.
1
1

ACCEPTED MANUSCRIPT
4
.2. Cyclic voltammetry
Electrochemical studies were carried out using IPC-Pro potentiostate in three-
electrode mode. The stationary glassy carbon (d = 2 mm) disk was used as working
electrode, the auxiliary electrode was a platinum-flag electrode. The reference electrode
was Ag/AgCl/KCl (sat.) with watertight diaphragm. All measurements were carried out
under argon. The samples were dissolved in the pre-deaerated solvent. The rate scan
-1
was 0.2 V·s . The supporting electrolyte 0.1 М Bu NClO (99%, «Acros») was
4
4
undergone twice recrystallization from aqueous EtOH and then it was dried in vacuum
-3
(
48h) under 50ºС. The concentration of complexes was 2ꢀ10 M.
4
.3. X-ray diffraction studies
The X-ray suitable crystals of complexes 3 and 6 were prepared by the prolonged
crystallization from n-hexane solution of complexes as solvate 3·0.167 hexane and 6.
X-ray diffraction data collected on a SMART APEX diffractometer (graphite-
monochromated, Mo -radiation, ω-scan technique, λ=0.71073 Å) at 100 K. The
Kα
intensity data were integrated by the SAINT program [15]. SADABS was used to
perform area-detector scaling and absorption corrections [16]. The structure was solved
2
by direct methods and was refined on F using the SHELXTL package [17]. All non-
hydrogen atoms were refined anisotropically.
Crystal data for C H F O Sb (3·0.167 hexane): M=623.70, crystal size 0.32 x 0.25 x
33
35.33
2
2
0
.18 mm, trigonal, space group R-3, a=36.976(3) Å, b=36.976(3) Å, c=11.2041(9) Å,
3
-1
α=β=90º, γ=120º, V=13265.9(19) Å , Z=18, F(000)=5730, d =1.405 g⋅cm , µ=0.976
calc
1
2

-1
mm , θ=2.22-26.00º, reflections collected 24871, independent reflections 5768
ACCEPTED MANUSCRIPT
2
(
R =0.0365), Completeness to θ=26.00º 99.4%, GOF(F )=1.202, R =0.0504 [I > 2σ(I)],
int
1
-3
wR =0.1088 (all data), largest diff. peak and hole 0.915/-0.444 e Å .
2
Crystal data for C H ClO Sb (6): M=607.79, crystal size 0.22 x 0.13 x 0.10 mm,
3
2
34
2
trigonal, space group R-3, a=36.5471(9) Å, b=36.5471(9) Å, c=11.4459(3) Å, α=β=90º,
3
-1
-1
γ=120º, V=13239.9(6) Å , Z=18, F(000)=5580, d =1.372 g⋅cm , µ=1.054 mm ,
calc
θ=2.46-26.00º, reflections collected 38292, independent reflections 5751 (R =0.0330),
int
2
Completeness to θ=26.00º 99.4%, GOF(F )=1.091, R =0.0338 [I > 2σ(I)], wR =0.0910
1
2
-3
(
all data), largest diff. peak and hole 1.102/-0.389 e Å .
CCDC 1486064 (3·0.167 hexane), 1486065 (6) contain the supplementary
crystallographic data for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre by www.ccdc.cam.ac.uk/data_request/cif.
4
.4. Syntheses
A solution of the corresponding triarylstibine (1 mmol) in 30 ml of toluene was
added dropwise with stirring to a toluene solution of 4,4-difluoro-3,6-di-tert-butyl-o-
benzoquinone (0.256 g, 1 mmol, 15-20 ml of toluene) till solution turned completely to
yellow-orange. Toluene was removed by evaporation under reduced pressure and
residue was dissolved in n-hexane (20 ml). The storage of the resulting solution at -
1
8°C for a day allowed to obtain bright yellow microcrystalline powders of complexes
1
-3. In all cases yields of aimed products were more 90%. Compounds are air-stable in
solid state and can be stored for a long time in the light-free conditions.
1
3

4
.4.1. Tris-p-fluorophenylantimony(V) 4,5-difluoro-3,6-di-tert-butylcatecholate (1): IR
ACCEPTED MANUSCRIPT
-1
(
nujol, cm ): 1647 w, 1585 s, 1492 s, 1451 m, 1432 m, 1407 s, 1391 m, 1362 m, 1303
w, 1278 m, 1262 m, 1233 s, 1204 w, 1161 s, 1092 m, 1063 m, 1044 s, 1020 m, 993 m,
9
5
61 s, 930 w, 890 m, 850 w, 825 s, 804 s, 772 w, 702 w, 674 w, 660 w, 631 m, 604 w,
1
82 w, 530 w, 509 s, 460 w, 435 w, 417 m. H NMR (400.1 MHz, CDCl , δ, ppm): 1.50
3
3
3
3
(
s, 18 H, 2 tBu), 7.21 (t, J = J = 8.6 Hz, 6 H, p-F-Ph), 7.70 (dd, J =8.2 Hz,
H,H
H,F
H,H
3
13
J =5.9 Hz, 6 H, p-F-Ph). C NMR (100.6 MHz, CDCl , δ, ppm): 30.98 (t, J =2 Hz,
H,F
3
C,F
CH tBu), 35.89 (s, C tBu), 116.82 (d, J =20.9 Hz, p-F-Ph), 120.21 (dd, J =3.2 Hz,
3
C,F
C,F
J =7.1 Hz, Ar), 132.20 (d, J =3.9 Hz, p-F-Ph), 136.80 (d J =8.1 Hz, p-F-Ph),
C,F
C,F
C,F
1
40.29 (t, J =6.1 Hz, Ar), 143.64 (dd, J =237.9 Hz, J =18.2 Hz, Ar), 164.85 (d,
C,F
C,F
C,F
19
J =252.9 Hz, p-F-Ph). F NMR (376.5 MHz, CDCl , δ, ppm): -106.96, -149.38. Anal.
C,F
3
Calc. for C H F O Sb (%): C, 57.94; H, 4.56; F, 14.32; Sb, 18.36. Found (%): C,
3
2
30
5
2
5
8.15; H, 4.71; Sb, 18.02.
4
.4.2. Tris-p-chlorophenylantimony(V) 4,5-difluoro-3,6-di-tert-butylcatecholate (2): IR
-1
(
nujol, cm ): 1647 w, 1570 s, 1478 s, 1452 w, 1435 m, 1405 s, 1381 m, 1361 m, 1340
w, 1303 w, 1275 m, 1263 m, 1238 w, 1201 w, 1184 w, 1090 s, 1062 s, 1044 s, 1011 s,
9
6
92 m, 961 s, 930 w, 889 m, 850 s, 810 s, 771 w, 726 s, 698 w, 674 w, 662 w, 633 m,
1
03 w, 581 w, 530 w, 522 w, 487 s, 460 w, 435 w, 418 w, 405 w. H NMR (400.1 MHz,
3
CDCl , δ, ppm): 1.50 (s, 18 H, 2 tBu), 7.49 (d, J =8.4 Hz, 6 H, p-Cl-Ph), 7.63 (d,
3
H,H
3
13
J =8.4 Hz, 6 H, p-Cl-Ph). C NMR (100.6 MHz, CDCl , δ, ppm): 30.99 (br.s, CH
H,H
3
3
tBu), 35.90 (s, C tBu), 120.32 (br. dd, Ar), 129.75 (s, p-Cl-Ph), 134.97 (s, p-Cl-Ph),
35.86 (s, p-Cl-Ph), 138.37 (s, p-Cl-Ph), 140.17 (br. s, Ar), 143.70 (dd, J =238.0 Hz,
1
C,F
1
4

19
J =18.3 Hz, Ar). F NMR (376.5 MHz, CDCl , δ, ppm): -149.13. Anal. Calc. for
C,F
3
ACCEPTED MANUSCRIPT
C H Cl F O Sb: C, 53.93; H, 4.24; Cl, 14.92; F, 5.33; Sb, 17.08. Found (%): C, 54.12;
3
2
30
3
2
2
H, 4.39; Sb, 16.83.
-
4
.4.3. Triphenylantimony(V) 4,5-difluoro-3,6-di-tert-butylcatecholate (3): IR (nujol, cm
1
): 1665 w, 1578 w, 1480 s, 1431 s, 1410 s, 1358 m, 1333 w, 1305 w, 1279 s, 1246 m,
1
202 m, 1181 w, 1158 w, 1097 w, 1070 m, 1058 m, 1046 s, 1023 w, 995 m, 963 w, 930
w, 891 s, 849 w, 799 w, 773 w, 734 s, 693 s, 673 w, 658 w, 623 m, 582 w, 523 m, 450 s,
1
4
22 w, 402 w. H NMR (400.1 MHz, CDCl , δ, ppm): 1.52 (s, 18 H, 2 tBu), 7.45-7.52
3
1
3
(
m, 9 H, Ph), 7.72-7.75 (m, 6 H, Ph). C NMR (100.6 MHz, CDCl , δ, ppm): 30.97 (t,
3
J =2.5 Hz, CH tBu), 35.87 (s, C tBu), 119.94 (dd, J =3.5 Hz, J =6.9 Hz, Ar),
C,F
3
C,F
C,F
1
29.23 (s, Ph), 131.25 (s, Ph), 134.85 (s, Ph), 137.40 (s, Ph), 140.64 (t, J =6.3 Hz,
C,F
19
Ar), 143.43 (dd, J =237.0 Hz, J =18.2 Hz, Ar). F NMR (376.5 MHz, CDCl , δ,
C,F
C,F
3
ppm): -150.22. Anal. Calc. for C H F O Sb (%): C, 63.07; H, 5.46; F, 6.24; Sb, 19.98.
32
33
2
2
Found (%): C, 62.95; H, 5.40; Sb, 20.21.
1
5

Acknowledgements
ACCEPTED MANUSCRIPT
A.I.P. is grateful to Russian Foundation for Basic Researches for the financial support
of the work (grant N 16-33-60157 mol_a_dk). The authors are grateful Russian
Foundation for Basic Researches (16-33-00027 mol_a) and the Council on Grants of
President of Russian Federation for support of young Russian scientists (MD-
7
347.2015.3).
Appendix A. Supplementary material
CCDC 1486064 (3·0.167 hexane), 1486065 (6) contain the supplementary
crystallographic data for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
1
13
19
Supplementary material contains H, C and F NMR spectra for complexes 1-3 and
Figure S10 of crystal cell and the hexamolecular macrocycle of 6.
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1
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[
[
[
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Bruker AXS, Madison, Wisconsin, USA(2000).
2
0

Table 1. The selected bond lengths and angles in complexes 3 and 6.
ACCEPTED MANUSCRIPT
3
6
Bond, Å
Bond, Å
Sb(1)-O(1)
Sb(1)-O(2)
Sb(1)-C(27)
Sb(1)-C(21)
Sb(1)-C(15)
F(1)-C(4)
F(2)-C(5)
O(1)-C(1)
O(2)-C(2)
C(1)-C(2)
C(1)-C(6)
C(2)-C(3)
C(3)-C(4)
C(4)-C(5)
C(5)-C(6)
2.006(2)
2.049(2)
2.100(3)
2.136(3)
2.143(3)
1.366(3)
1.425(4)
1.358(3)
1.357(4)
1.395(5)
1.405(4)
1.404(4)
1.387(5)
1.368(5)
1.392(4)
Sb(1)-O(1)
Sb(1)-O(2)
Sb(1)-C(15)
Sb(1)-C(21)
Sb(1)-C(27)
Cl(1)-C(4)
2.0417(14)
2.0131(14)
2.1400(19)
2.135(2)
2.099(2)
1.765(2)
O(1)-C(1)
O(2)-C(2)
C(1)-C(2)
C(1)-C(6)
C(2)-C(3)
C(3)-C(4)
C(4)-C(5)
C(5)-C(6)
1.361(2)
1.363(2)
1.407(3)
1.398(3)
1.410(3)
1.399(3)
1.387(3)
1.387(3)
Angle, º
Angle, º
O(1)-Sb(1)-O(2)
O(2)-Sb(1)-C(27)
O(1)-Sb(1)-C(27)
O(1)-Sb(1)-C(21)
O(2)-Sb(1)-C(21)
77.84(8)
97.53(10)
O(1)-Sb(1)-O(2)
O(2)-Sb(1)-C(27) 106.42(7)
78.13(6)
109.20(11) O(1)-Sb(1)-C(27) 98.43(7)
142.10(9)
87.80(11)
O(1)-Sb(1)-C(21) 154.97(8)
O(2)-Sb(1)-C(21) 83.20(7)
C(21)-Sb(1)-C(27) 107.33(12) C(21)-Sb(1)-C(27) 102.77(8)
O(1)-Sb(1)-C(15)
O(2)-Sb(1)-C(15)
C(21)-Sb(1)-C(15) 98.27(12)
83.27(10)
155.87(10) O(2)-Sb(1)-C(15) 143.68(7)
C(21)-Sb(1)-C(15) 98.64(8)
C(27)-Sb(1)-C(15) 102.81(11) C(27)-Sb(1)-C(15) 108.45(8)
O(1)-Sb(1)-C(15) 86.98(7)
2
1

-1
Table 2. The CV data on complexes 1-8 (GC electrode, CH Cl , V = 0.2 Vꢀs , 0.1 М
2
2
ACCEPTED MANUSCRIPT
-3
NBu ClO , С = 2ꢀ10 M, Ar, vs. Ag/AgCl/KCl (sat.)).
4
4
1
2
Compound
N
1
2
3
4
5
6
7
8
Е
1/2, V
Iс/Iа
n
1
Е , V
p
(
(
(
(
(
(
(
(
4,5-F-3,6-Cat)Sb(p-F-Ph)3
4,5-F-3,6-Cat)Sb(p-Cl-Ph)3
4,5-F-3,6-Cat)SbPh3
0.92
0.91
0.90
0.95
0.97
0.98
0.90
0.89
0.97
0.92
0.92
0.70
0.71
0.81
0.71
0.82
1.34
1.39
1.36
1.43
1.46
1.37
1.40
1.40
1
1
4-Cl-3,6-Cat)Sb(p-F-Ph)3 [6d]
4-Cl-3,6-Cat)Sb(p-Cl-Ph)3 [6d]
1
n>1
1
4-Cl-3,6-Cat)SbPh3
3,6-Cat)Sb(p-F-Ph)3
3,6-Cat)SbPh3
[6a]
[7a]
[6a]
1
1
1
2
Note: E – the half-wave potential of the first anodic process; E – the oxidation peak
1/2
p
potential of the second anode stage; I /I – the current ratio of reverse cathodic and
c
a
direct anode peaks; n - number of electrons transferred in the redox process vs.
ferrocene.
2
2

Captures to figures
ACCEPTED MANUSCRIPT
1
3
Figure 1. The aromatic region of C NMR spectrum of complex (4,5-F -3,6-Cat)Sb(p-
2
F-Ph) (1) (CDCl , 200 MHz, RT).
3
3
Figure 2. Molecular structures of (4,5-F -3,6-Cat)SbPh (3) (top) and (4-Cl-3,6-
2
3
Cat)SbPh (6) (bottom) in crystals with the thermal ellipsoids of 30% probability. The
3
hydrogen atoms are omitted for clarity.
Figure 3. The crystal cell of (4,5-F -3,6-Cat)SbPh (3) (top) and the hexamolecular
2
3
macrocycle [(4,5-F -3,6-Cat)SbPh ] (bottom).
2
3 6
Figure 4. The CV curve of (4,5-F -3,6-Cat)Sb(p-F-Ph) (1): 1 – the potential switch
2
3
from -0.70 to +1.20 V; 2 – the potential switch from -0.70 to +1.70 V (CH Cl , GC
2
2
-3
-1
electrode, C = 2ꢀ10 M, 0.1 М NBu ClO , V = 0.2 Vꢀs , vs. Ag/AgCl/KCl(sat.)).
4
4
2
3

Synopsis
ACCEPTED MANUSCRIPT
Novel triarylantimony(V) 4,5-difluoro-3,6-di-tert-butylcatecholates have been synthesized. Their
electrochemical oxidation proceeds as two consecutive stages with formation of stable mono- and
unstable dicationic derivatives. The fluorine substituents in Cat ligand behave as weak donors with
positive mesomeric effect: the first oxidation potential “Cat/SQ” is only insufficiently shifted to the
anodic region, while the second oxidation step “SQ/Q” is facilitated. Complexes (4,5-F -3,6-Cat)SbPh3
2
and (4-Cl-3,6-Cat)SbPh form an unusual hexamolecular core [CatSbPh ] in crystals.
3
3 6
Graphical abstract
2
4

ACCEPTED MANUSCRIPT
Highlights
New triarylantimony(V) 4,5-difluoro-3,6-di-tert-butylcatecholates (F -3,6-Cat)SbAr .
2
3
+
An increased stability of electrogenerated monocationic forms [(F -3,6-SQ)SbAr ] .
2
3
A weak influence of fluorine atoms on the first oxidation potential (Cat/SQ).
Difluoro- and chloro-substituted catecholates form hexamolecular macrocycle.

ACCEPTED MANUSCRIPT
Supplementary material
Content:
1
Figure S1. The H NMR spectrum of (4,5-F -3,6-Cat)Sb(p-F-Ph) (1) (CDCl , 296 K).
2
2
3
3
1
3
Figure S2. The C NMR spectrum of (4,5-F -3,6-Cat)Sb(p-F-Ph) (1) (CDCl , 296 K).
3
2
3
3
1
9
Figure S3. The F NMR spectrum of (4,5-F -3,6-Cat)Sb(p-F-Ph) (1) (CDCl , 296 K).
4
2
3
3
1
Figure S4. The H NMR spectrum of (4,5-F -3,6-Cat)Sb(p-Cl-Ph) (2) (CDCl , 296 K).
5
2
3
3
1
3
Figure S5. The C NMR spectrum of (4,5-F -3,6-Cat)Sb(p-Cl-Ph) (2) (CDCl , 296 K).
6
2
3
3
1
9
Figure S6. The F NMR spectrum of (4,5-F -3,6-Cat)Sb(p-Cl-Ph) (2) (CDCl , 296 K).
7
2
3
3
1
Figure S7. The H NMR spectrum of (4,5-F -3,6-Cat)SbPh (3) (CDCl , 296 K).
8
2
3
3
1
3
Figure S8. The C NMR spectrum of (4,5-F -3,6-Cat)SbPh (3) (CDCl , 296 K).
9
2
3
3
1
9
Figure S9. The F NMR spectrum of (4,5-F -3,6-Cat)SbPh (3) (CDCl , 296 K).
10
2
3
3
Figure S10. The crystal cell of (4-Cl-3,6-Cat)SbPh (6) (top) and the hexamolecular macrocycle
3
[
(4-Cl-3,6-Cat)SbPh ] (bottom).
11
3
6
1

ACCEPTED MANUSCRIPT
1
Figure S1. The H NMR spectrum of (4,5-F -3,6-Cat)Sb(p-F-Ph) (1) (CDCl , 296 K).
2
3
3
2

ACCEPTED MANUSCRIPT
1
3
Figure S2. The C NMR spectrum of (4,5-F -3,6-Cat)Sb(p-F-Ph) (1) (CDCl , 296 K).
2
3
3
3