New oxidovanadium(iv) complex with a BIAN ligand: synthesis, structure, redox properties and catalytic activity

Article abstract of DOI:10.1039/C8NJ03358G

Reaction of VCl₃ with bis[N-(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) in air afforded [VOCl₂(dpp-bian)] (1). The complex was characterized by IR and UV-vis spectroscopies and elemental analysis. The crystal structure of 1 was determined by X-ray diffraction (XRD) analysis. The vanadium atom is in a square-pyramidal OCl₂N₄ coordination environment. The cyclic voltammogram (CV) in dichloromethane reveals an irreversible oxidation process at +1.40 V (vs. Ag/AgCl) assigned to the V(iv)/V(v) couple, and two consecutive quasi-reversible one-electron reduction processes at ?0.32 V and ?1.05 V (vs. Ag/AgCl), respectively, assigned to the bian/bian^?/ and bian^?//bian^2? couples, followed by irreversible reduction at ?1.6 V (vs. Ag/AgCl). The EPR spectrum of 1 in toluene shows a single 8-line signal typical for oxidovanadium(iv) complexes with d¹ configuration. The magnetic behavior of 1 confirms the presence of one unpaired electron (μ_eff (330 K) = 1.67 μ_B), and the isolation of the paramagnetic centers. Application of 1 to oxidation of alkanes documented high catalytic activity under mild conditions. The kinetics and selectivity of alkane oxygenation by the 1/H₂O₂ and 1/PCA/H₂O₂ systems (PCA is pyrazine-2-carboxylic acid) were studied. The reaction is more efficient in the presence of PCA.

Full text of DOI:10.1039/C8NJ03358G

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Gushchin, L. S. Shul'pina, N. S. Ikonnikov, P. A. Abramov, N. Romashev, A. Poryvaev, A. Sheveleva, A. S.
Bogomyakov, N. Shmelev, M. V. Fedin, M. N. Sokolov and G. B. Shul'pin, New J. Chem., 2018, DOI:
1
0.1039/C8NJ03358G.
Volume 40 Number
1
January 2016 Pages 1–846
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PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
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rsc.li/njc

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…
……………………………………………………………..
New oxidovanadium(IV) complex with redox-active
acenaphthene-1,2-diimine ligand: synthesis, structure,
redox properties and catalytic activity in alkane
oxidations with hydrogen peroxide †
a
ab
c
c
Iakov S. Fomenko, Artem L. Gushchin,* Lidia S. Shul’pina, Nikolay S. Ikonnikov,
a
ab
bd
bd
Pavel A. Abramov, Nikolay F. Romashev, Artem S. Poryvaev, Alena M. Sheveleva,
d
ab
d
ef
Artem S. Bogomyakov, Nikita Y. Shmelev, Matvey V. Fedin, Georgiy B. Shul’pin,*
and Maxim N. Sokolov
ab
___________________________________________________________________________
a
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3 Acad. Lavrentiev Ave.,
Novosibirsk 630090, Russia. E-mail: gushchin@niic.nsc.ru
b
Novosibirsk State University, 2 Pirogov Str., 630090 Novosibirsk, Russia
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ulitsa Vavilova, dom 28, Moscow
c
1
19991, Russia ORCID Lidia S. Shul'pina: http://orcid.org/0000ꢀ0002ꢀ1448ꢀ9228
International Tomography Center, Siberian Branch of Russian Academy of Sciences, 3a Institutskaya st., 630090 Novosibirsk,
d
Russia
e
Department of Dynamics of Chemical and Biologicl Processes, Semenov Institute of Chemical Physics, Russian Academy of
Sciences, ulitsa Kosygina, dom 4, Moscow 119991, Russia. Email: shulpin@chph.ras.ru ORCID: http://orcid.org/0000-0002-
7
053-4812
f
Chair of Chemistry and Physics, Plekhanov Russian University of Economics, Stremyannyi pereulok, dom 36, Moscow 117997,
Russia
†
Electronic supplementary information (ESI) available: details of kinetic study. For ESI and crystallographic data in CIF or
other electronic format see DOI: xxxxxxxx
<Abstract:>
Reaction of VCl
3
with bis[Nꢀ(2,6ꢀdiisopropylphenyl)imino]acenaphthene (dppꢀbian) in air afforded
[
VOCl (dppꢀbian)] (1). The complex was characterized by IR and UVꢀvis spectroscopies and elemental
analysis. The crystal structure of 1 was determined by Xꢀray diffraction (XRD) analysis. The vanadium
atom is in a squareꢀpyramidal OCl coordination environment. Cyclic voltammogram (CV) in
2
2
N
4
dichloromethane reveals irreversible oxidation process at +1.40 V (vs. Ag/AgCl) assigned to the
V(IV)/V(V) couple, and two consequtive quasiꢀreversible oneꢀelectron reduction processes at ꢀ0.32 V and
ꢀ/⋅
ꢀ/⋅
2ꢀ
ꢀ
1.05 V (vs. Ag/AgCl), respectively, assigned to the bian/bian and bian /bian couples, followed by
irreversible reduction at ꢀ1.6 V (vs. Ag/AgCl). EPR spectrum of 1 in toluene shows a single 8ꢀline signal
1
typical for oxidovanadium(IV) complexes with d configuration. Magnetic behavior of 1 confirms the
presence of one unpaired electron (ꢁeff (330 K) = 1.67 ꢁ
B
), and the isolation of the paramagnetic centers.
1

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Application of 1 to oxidation of alkanes documented high catalytic activity under mild conditions.
Kinetics and selectivity of alkanes oxygenation by the 1/H and 1/PCA/H systems (PCA is
pyrazineꢀ2ꢀcarboxylic acid) were studied. The reaction is more efficient in the presence of PCA.
2
O
2
2 2
O
1. Introduction
Numerous catalytic processes require metalꢀbased oxidation state changes to facilitate desirable
chemical transformations. Transition metal complexes with redoxꢀactive ligands have attracted
considerable interest for use in multiꢀelectron activation of small molecules and redoxꢀbased catalytic
1
–8
reactions . Redoxꢀactive ligands have more energetically accessible levels for reduction or oxidation. As
a result, either exclusively ligandꢀcentered redox processes can occur, with the metal center remaining in
the same oxidation state, or both the ligand and metal change their oxidation state in a synergistic fashion,
creating ambiguity about the electronic state of both metal and ligand. Nature employs this feature in
various metalloenzymes wherein the active site contains a redoxꢀactive ligand that works in synergy with
9,10
a metal ion
Bis(imino)acenaphthenes (BIANs) are highly conjugated, redox active, and sterically bulky αꢀ
.
11ꢀ32
diimines which are widely used as bidentate ligands in coordination chemistry and catalysis
. Similar
to their dithiolene and dioxolene counterparts, these redoxꢀactive ligands are able to coordinate to metal
centers in multiple oxidation states and have even been shown to facilitate internal electron transfer
33–36
(
redox isomerism)
Despite the fact that BIAN ligands are a fairly wellꢀknown class of ligands and there are many
complexes with transition metals, vanadium complexes with BIAN ligands are extremely rare. Bendix et
.
3
3
al. have recently reported homoleptic vanadium complexes [V(dmpꢀbian) ] and [V(dmpꢀbian) ](PF ) .
3
3
6
Two discrete redox isomers were identified for the latter one, demonstrating a rare example of valence
IV
tautomerism in vanadium complexes. Some mixedꢀligand oxidovanadium(IV) complexes [V O(acac)(Rꢀ
bian)]Cl (R = H, CH , Cl) have also been reported without structural characterization. These complexes
3
promote catalytic oxidation of cyclohexene, cisꢀcyclooctene and styrene with both tertꢀ
3
0
2 2
butylhydroperoxide and H O .
Organic and inorganic peroxides and especially hydrogen peroxide are widely employed for
oxidation of various classes of organic compounds. Even alkanes are among those substrates, despite
being generally highly resistant to reactions under mild conditions. In recent decades many metal
3
7–41
complexes have been described as catalysts in alkane oxygenation with dioxygen or peroxides
.
One of the first such systems, doing oxidation with the participation of hydroxyl radicals, is the
42–44
combination of H
2
O
2
with an iron salt. In the case of Fe(II) this is “Fenton reagent”
. In the course of
3+
3+
·
+
2+
the hydrogen peroxide oxidation by Fe ion, according to the equation H
2
O
2
+ Fe = HOO + H + Fe ,
2

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the stoichiometric Fenton system, “Fe(II)–H O ”, is transformed gradually into the catalytic system
2
2
“
2 2
Fe(III)–Fe(II)–H O ” (“Fentonꢀlike” or “Fentonꢀtype” system). Fenton reaction proceeds in accordance
with the following equation:
3
+
2+
·
–
H
2
O
2
+ Fe = Fe + HO + HO
Usually, simple metal salts are poor catalysts, but their activity becomes much higher if certain coꢀ
4
5
catalysts are added to the reaction solution .
4
6–52
Vanadium ions constitute the reaction centres of certan enzymes
, and soluble or
heterogeneous vanadium derivatives are efficient reagents and catalysts in oxygenation of various organic
53–59
compounds, particularly, hydrocarbons (see selected reviews
).
a reagent based on a vanadium derivative in
6
0–78
Earlier some of us have discovered and studied
combination with pyrazineꢀ2ꢀcarboxylic acid (PCA), which efficiently oxidizes alkanes in acetonitrile
solution at low temperatures. Some vanadium catalysts did not require the presence of PCA in the
reaction solution. Two crucial stages (see above) in catalytic oxidation with the Fenton system are
V
IV
·
+
IV
V
·
–
analogous to the steps V + H
2 2 2 2
O = V + HOO + H and V + H O = V + HO + HO proposed for
V
IV
the oxidation with the “O + H O + nꢀBu NVO + PCA” reagent. Here ions V and V correspond,
2
2
2
4
3
III
II
respectively, to Fe and Fe . It was proposed that the important stage of the reaction is proton transfer
from coordinated H molecule to the oxo (=O) or peroxo (OꢀO) or hydroxy (OH) ligand at vanadium
2 2
O
ion. One route is pcaꢀassisted mechanism (“robot’s arm mechanism; pce is the anion of PCA), and the
second pathway is waterꢀassisted mechanism. Both routes were confirmed with DFT calculations.
In this work we report preparation, structure, redox behavior, and сatalytic properties in alkane
2
oxidation of novel oxidovanadium(IV) complex [VOCl (dppꢀbian)] (1) with bis(Nꢀ(2,6ꢀ
diisopropylphenyl)imino)cenaphthene (dppꢀbian) ligand. The is the first oxidovanadium complex
containing a bis(arylimino)acenaphthylene type ligand.
2. Results and discussion
2.1. Synthesis and characterization of 1
The target complex was obtained by using vanadium trichloride (VCl
3
) as starting compound, which is
oxidized during the reaction in air to give the V=O moiety. This synthetic procedure was previously
applied by for the synthesis of other oxidovanadium(IV) complexes with dehydrophenanthroline and
79
diazofluorene ligands . The reaction of VCl
3
with bis(Nꢀ(2,6ꢀdiisopropylphenyl)imino)acenaphthene
(
dppꢀbian) results in [VOCl (dppꢀbian)] (1) in 50% yield (Scheme 1).
2
3

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Scheme 1
IR spectrum of 1 reveals typical vibration bands of the CH group in the region of 2965ꢀ2869 cm ,
ꢀ1
ꢀ1
and of CC and CN groups in the region of 1641ꢀ1008 cm of the dppꢀbian ligan, as well as the
ꢀ1
ꢀ1
characteristic band of the V=O group at 997 cm . The bands at 1641 and 1625 cm assigned to ν(C=N)
vibrations are expectedly shifted to lower wavenumbers from those for free dppꢀbian (1671, 1652, 1642
ꢀ1 30
ꢀ1
cm ) . The ν(V=O) stretching mode appears as a strong band at 997 cm , in agreement with the V=O
80,81
stretching frequencies reported for other oxidovanadium(IV) complexes
.
Electronic spectrum of 1 in CH Cl displays strong absorption bands in the range of 275ꢀ495 nm
2
2
due to intraligand, ligandꢀtoꢀmetal and metalꢀtoꢀligand charge transfer transitions.
2
.2 Crystal structure of 1·1.7CH
Single crystals of 1·1.7CH Cl suitable for Xꢀray analysis were obtained by recrystallization of 1 from
CH Cl /hexane mixture. The molecular structure of 1 is shown in Fig. 1. Selected bond distances and
2 2
Cl
2
2
2
2
angles are listed in Table 2. The coordination environment around vanadium is a distorted squareꢀ
pyramid, where the two N and two Cl atoms define the equatorial plane, while the oxygen atom occupies
the axial position. The vanadium atom lies about 0.516 Å above the equatorial plane. The preference for a
squareꢀpyramidal geometry may be caused, in addition to strong transꢀeffect of the V=O bond, by the
presence of two bulky 2,6ꢀdiisopropylphenyl groups in dppꢀbian which block the coordination of the
solvent molecule (CH
in LVOCl (L = HB(Me
The V=O bond lengths of 1.567 (7) and1.587 (8) Å lie within the range 1.56ꢀ1.63 Å reported for
3 2
CN). The squareꢀpyramidal coordination in VOCl complexes has also been found
8
2
83
84
2
2 3 2 2 2 2
pz) ) , [VOCl (tmen)] , VOCl (NHMe ) .
85
other oxidovanadium(IV) complexes . The VꢀCl (2.279(3)ꢀ2.295(3) Å) and VꢀN (2.136(9)ꢀ2.176(8) Å)
bond lengths are also similar to those found elsewhere. The bond lengths of the N=C–C=N moiety are
indicative of a C–C single bond and two C=N double bonds, which is in full agreement with the
10,75,76
formulation of a neutral 1,2ꢀdiimine ligand
.
4

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2
Fig. 1. ORTEP representation (50% probability ellipsoids) of [VOCl (dppꢀbian)] (1)
2.3. The cyclic voltammogram for 1
The cyclic voltammogram for 1 in CH Cl reveals two quasiꢀreversible reduction processes at ꢀ0.32 V
2
2
(ꢂE = 0.10 V) and ꢀ1.05 V (ꢂE = 0.23 V) vs. Ag/AgCl (Fig. 2), and subsequent irreversible reduction at ꢀ
ꢀ/⋅
1
.5 V. The first two processes are presumably ligandꢀcentered and can be assigned to the bian/bian and
ꢀ/⋅
2ꢀ
bian /bian couples in accordance with the ability of the acenaphthene diimine moiety to accept two
88–91
electrons to give acenaphthylene diamide dianion
reduction wave documented with E /E value of ꢀ1.64/ꢀ2.11 V (vs. Fc/Fc ) in CH Cl
2
. Free dppꢀbian ligand was shown to give a single
+
26,91
.Subsequent
a
c
2
reduction wave ꢀ1.5 V for 1 is assigned to the conversion of V(IV) to V(III), which is typically
irreversible because it entails loss of the vanadyl oxygen. An additional anodic peak at around ꢀ0.07 V
was also observed on CV, and it becomes weaker in a narrower potential window (red line on Fig. 2).
This may indicate the generation of an electroactive species upon further transformation of the reduction
product formed on the second reduction step.
In the anodic part an irreversible oxidation at +1.40 V was detected, probably due to oneꢀelectron
IV
92
2
oxidation of V(IV) to V(V). Similar oxidation process has been found for V O(acac) .
5

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Fig. 2. Cyclic voltammograms of 1 в CH
2 2
Cl in the ranges from +0.20 to ꢀ2.00 V (blue line) and from
+0.20 to ꢀ1.00 V (red line) at scan rate of 0.1 V/s
2.4. Magnetic susceptibility measurements
Static magnetic susceptibility measurements for 1 were carried out in the range 2ꢀ300 K. At 300 K the
effective magnetic moment (ꢁ ) is 1.67 ꢁ , and this value does not change with lowering temperature
eff
B
(Fig. 3). The 1/χ(T) dependence obeys the CurieꢀWeiss law, best fitted with the Curie and Weiss
3
constants of 0.347 cm
⋅K/mol and 0.1 K, respectively. The ꢁeff and Curie constant values agree well with
3
the theoretical spin only ones (1.73ꢁ
B
and 0.375 cm
⋅K/mol) for single paramagnetic center with S = 1/2
and g = 2. The permanency of ꢁeff in a wide temperature range and the small value of the Weiss constant
indicate absence of significant exchange interactions and the isolation of paramagnetic centers.
6

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3
ꢀeff ꢀB
,
1/χ, mol/cm
2
.0
.9
.8
.7
.6
.5
.4
.3
800
600
400
200
0
1
1
1
1
1
1
1
0
100
200
300
T, K
Fig. 3. Temperature dependencies of the µeff (●) and 1/χ (■) for 1. Solid line is a theoretical curve
2.5. The EPR spectra
The EPR spectra of 1 in toluene and solid state detected at room temperature are presented on Fig. 4. The
IV
1
spectrum in solution presents eightꢀline isotropic signal characteristic for V (d ). In solid state the
spectrum is noticeably broader and anisotropic due to molecular rigidity. For both cases simulation
analysis showed the following gꢀ and Aꢀtensor values: g
⊥
= 1.972 and g∥= 1.954, the hyperfine interaction
ꢀ4
ꢀ1
ꢀ4
ꢀ1
(HFI) tensor A
⊥
= 58.8 × 10 cm , A
∥
= 162 × 10 cm . These values are typical for oxidovanadium(IV)
93
complexes .
Fig. 4. XꢀBand CW EPR spectra of complex 1: (a) in toluene, (b) in solid state. All spectra are scaled for
the maximum EPR intensity to be 1. All EPR measurements were carried out at 298 K. Simulations are
shown in red
7

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2.6 Oxygenation of alkanes
Alkanes are oxidized in acetonitrile solution to alkyl hydroperoxides by hydrogen peroxide in air in the
presence of catalytic amounts of complex 1. We studied the oxygenation of cyclic, linear and branched
2 2 2 2
alkanes with the 1/H O and 1/PCA/H O systems (where PCA or Hpca is pyrazineꢀ2ꢀcarboxylic acid) in
acetonitrile solution under mild conditions (typical temperature 40ꢀ50°C). The obtained data are
demonstrated in Figs. 5ꢀ7. Kinetic curves obtained for the formation of oxygenates from cyclohexane
(Fig. 5, Graph A) indicate that the oxidation is very efficient and may be compared with the reaction with
the H /nꢀBu NVO /PCA system (Fig. 5, Graph C).
O
2 2
4
3
8

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1a
A
0
0
0
0
.08
.06
.04
.02
0
2
a
1
2k
k
0
.14
.12
.10
.08
B
0
1a
0
0
0.06
0.04
0.02
0
2
a
1k
2k
0.12
0.10
0.08
C
1a
0.06
0.04
0.02
0
1
k
2
2k
a
0
1
2
3
4
5
6
Time (h)
Fig. 5. Oxygenation of cyclohexane in the presence of PCA (curves 1) or in the absence of PCA (curves
) with the H O /1 (curves 2) and H O /1/PCA (curves 1) systems. Each point corresponds to the
2
2
2
2
2
concentrations of either cyclohexanol (marked by letter a) or cyclohexanone (marked as k) measured after
–
4
reduction of the reaction sample with PPh
3
. Conditions for Graph A: [catalyst 1]
0
= 1.0 × 10 M, [PCA]
0
=
0.0004 M; [H O ] = 2.0 M (50% aqueous), [cyclohexane] = 0.46 M; MeCN up to total volume 5 mL;
2 2 0 0
–4
–3
50 °C. Conditions for Graph B: [catalyst 1]
0
= 5.0 × 10 M, [PCA]
0
= 2.0 × 10 M; [H
2
O
]
2 0
= 2.0 M
9

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(
50% aqueous), [cyclohexane] = 0.46 M; MeCN up to total 5 mL volume; 50 °C. For comparison the
0
–
reaction catalysed by nꢀBu
4
NVO
3
(Graph C). Conditions for Graph C: catalyst [nꢀBu
= 2.0 M (50% aqueous), [cyclohexane]
4 3 0
NVO ] = 1.0 × 10
4
M, [PCA]
0
= 0.0004 M; [H
2
O
2
]
0
0
= 0.46 M; MeCN up to total 5
mL volume; 50 °C.
In order to get insight into the mechanism of the oxygenation we made special experiments using
94
tests which allow us to demonstrate the participation of hydroxyl radicals in these reactions .
2
.6.1 A comparison of chromatograms obtained before and after reduction with PPh
The samples obtained in the alkane oxidation were routinely analyzed both before and after their
treatment with PPh by GC. This method (the comparison of chromatograms of the same sample obtained
before and after addition of PPh ) was proposed by one of us earlier (the Shul’pin method)
3
3
41,94–102
, allows
3
estimation of the real concentration of an alkyl hydroperoxide, ketone (aldehyde), and alcohol present in
the reaction solution.
Addition of solid PPh to the aliquot taken from the reaction mixture immediately quenches the
3
reaction. In experiments without PPh
3
, the reaction was quenched by rapid cooling to the room
(see examples of nꢀheptane and
temperature. Samples for the analysis with and without PPh
3
methylcyclohexane, MCH, oxidations in the ESI, Fig. S2) were taken simultaneously. Attribution of the
peaks was made by comparison with the chromatograms of authentic samples and by GCꢀMS. The
formation of alkyl hydroperoxide detected by use of the Shul’pin method testifies that in the oxidation
reaction an alkane, RH, is transfomed into the corresponding alkyl radical, R•, which rapidly captures
molecular oxygen. Peroxyl radical ROO•, thus formed, can further be reduced to alkyl hydroperoxide,
ROOH.
2
.6.2 A competition of RH and MeCN for hydroxyl radical
The dependence of W on the initial concentration of cyclohexane is shown in Fig. 6 (Graph A). It can be
seen that the rate W is approaching to a plateau at relatively high concentrations of cyclohexane. The
0
0
dependence reflects the competition between cyclohexane and acetonitrile. For treatment of the data
shown in Fig. 6 we applied the following kinetic scheme:
ki
H
2
O
2
+ 1
HO•
(i)
kRH
HO• + RH
ROOH
(1)
(2)
kMeCN
HO• + MeCN
products
10

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Here (i) is the reaction of hydroxyl radical generation; (1) is the process of RH transformation into ROOH
with a bimolecular interaction between HO• and RH as the rateꢀlimiting stage; (2) is the process of
acetonitrile oxidation with the participation of hydroxyl radicals (a bimolecular interaction between HO•
and CH
3
CN as the rateꢀlimiting stage). The analysis of experimental data given in Fig. 6A led to a straight
–
0
1
–1
line corresponding to the linear dependence of W
on [CyH]
0
(Fig. 6, Graph B). Accepting [MeCN] ≈
–3
1
8 M we can obtain the ratio k /k ≈ 8.3·× 10 . The value of this parameter is in agreement with the
2 1
1
03,104
assumption about the participation of hydroxyl radicals (Table S1, see refs
).
7
A
6
5
W0− × 10−5 (M s)
1
−1
4
3
2
B
0
.30
0
.20
0
2
4
6
8
−
1
−1
1
0
[cyclohexane]0 (M )
0
0.2
0.4
0.6
0.8
Concentration [cyclohexane]0 (M)
Fig. 6. Dependence of the initial oxidation rate W on initial concentration of cyclohexane in the
0
–4
–3
cyclohexane oxidation in acetonitrile (Graph A) Conditions: [1]
= 2 M (50% aqueous), 50°C. Concentrations of oxygenates (sum of cyclohexanol and
cyclohexanone) were measured after reduction with PPh . Linear anamorphosis of the curve shown in
0 0
= 5.0·× 10 M; [PCA] = 2 × 10 M;
2 2 0
[H O ]
3
–
1
–1
Graph A is presented in Graph B in the coordinates [cyclohexane]
0 0
–W
2.6.3 An effect of added benzene
As shown in Fig. 7, addition of benzene (0.23 M) to the solution of cyclohexane (0.23 M) only very
slightly decreases the initial oxidation rate. Earlier some of us demonstrated that benzene does not affect
1
2
05
106
2
oxidation in the reaction of cyclohexane with Os complex/H
2
O
, copper silsesquioxane/H
2
O
,
107
ferrocene/H O systems . It has been found that all these systems operate with the generation of
2
2
hydroxyl radicals. The benzene hydroxylation with H
2
O
2
occurs with the formation of hydroxyl
1
08
radicals . Active species Fe(IV)=O was proposed for the case of benzene hydroxylation in ionic
109,110
liquids
. It has been shown that reactions of hydroxyl radical with benzene were faster in water than
111
in acetonitrile, by a significant factor of 65 (Ref. ). Indeed, the catalytic activity was significantly
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112
improved by adding water to acetonitrile solvent . These data can explain a weak effect of added
benzene in the cyclohexane oxidation in acetonitrile catalyzed by complex 1.
0.03
1
0.02
2
0.01
0
0
10
20
30
40
Time (min)
Fig. 7. Accumulation of cyclohexanol and cyclohexanol (a sum) in the initial period after treating with
PPh in the cyclohexane oxidation in acetonitrile in the absence of benzene (curve 1) and in the presence
of benzene (curve 2). Conditions: [1]
.23 M, [benzene] = 0.23 M (for curve 2 only), 40°C. Concentrations of oxygenates (sum of
3
–
4
0
2 2 0 0
= 5.0·× 10 M; [H O ] = 2 M (50% aqueous), [cyclohexane] =
0
0
cyclohexanol and cyclohexanone) were measured after reduction with PPh
3
2
.6.4 Selectivity parameters
The selectivity parameters in the of alkane oxygenation reactions with oxygenation by the 1/H
/PCA/H O systems correspond to the selectivity typical for the reactions with the participation of
2
2
O and
1
2
2
1
04
hydroxyl radicals (Table S2) . To compare these data, the corresponding parameters for some other
systems are also given in Table S2. For example, the oxidation by hydrogen peroxide in air under UVꢀ
irradiation or in the presence of a Fe(II) salt (the Fenton reagent) proceeds via the formation of hydroxyl
radicals which attack C–H bonds of the alkane. The selectivity parameters for the oxidation by the
–
3
H
2
O
2
/VO
/PCA system are also low. Other systems, which oxidize with the participation of hydroxyl
radicals are listed in Table S2. In the case of 1 the selectivity parameters for nꢀheptane are low,
C(1):C(2):C(3):C(4) ≈ 1.0:5.6:5.8:5.5. Unlike all these systems, alkane oxygenation reactions by the
IV
IV
2+
H
2
O
2
/[(TMTACN)Mn (
ꢀ
ꢀO)
3
Mn (TMTACN)] /CH
3
COOH H
2
O
2
/complex 2/oxalic acid systems
Me2R
3+
Me2R
(
complex 2 is [Mn
2
(RꢀL
)
2
(ꢀ
ꢀO)
2
]
where RꢀL
= (R)ꢀ1ꢀ(2ꢀhydroxypropyl)ꢀ4,7ꢀdimethylꢀ1,4,7ꢀ
104,113
V
triazacyclononane.)
In summary, it follows from Table S2 that the oxidation by the 1/H
low selectivities for nꢀheptane and a branched alkane and the reaction with isomers of 1,2ꢀ
apparently involve the interaction of the C–H bonds with Mn =O species.
2
2
O /PCA system exhibits very
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dimethylcyclohexane is not stereoselective. These data testify clearly that alkane oxygenation with the
1
2 2
/H O /PCA system proceeds mainly with the participation of free hydroxyl radicals.
2.6.5 A possible mechanism of hydroxyl radical generation
59–66,69–78
A tentatively proposed simplified catalytic cycle is presented in Scheme S1
. This scheme is
based on our previous kinetic and DFT results on alkane oxidation catalysed by various vanadium
complexes. We should take into account the fact that in the catalysis by complex 1 addition of PCA
2 2
accelerates the alkane oxidation (as in the case the reaction with the vanadate/PCA/H O system)
although in the absence of PCA sufficient amounts of the oxygenates are also produced. The mechanism
of the HO• formation appears to be different from those usually accepted for the Fenton or Fentonꢀlike
systems. The redox active ligand in the catalyst molecule but not the metal center plays the crucial role in
•
the generation of HO radicals from H O and, therefore, in the oxidation of alkanes. The DFT
2
2
60
•
calculations allowed us to assume the mechanism of the HO generation without a direct involvement of
114–116
the metal center developed previously for nonꢀtransition metal complex catalysts
. The activation of
H O toward homolysis occurs upon coordination of hydrogen peroxide to the metal center of the catalyst
2
2
molecule and does not require the change of the metal oxidation state and formation of the HOO·radical.
Such activation is associated with the redoxꢀactive nature of the dppꢀbian ligand. One of the key points of
the successful use of complex 1 in the catalytic oxidation of alkanes is the phenomenon of "activating
2
complexation" in the BIANꢀV(O)Cl system. Such effect is known for complexes of flavins, quinones.
Effects of metal ions on thermal and photoinduced electronꢀtransfer reactions from electron donors, D, to
electron acceptors, A, has been reviewed in terms of metal ionꢀcoupled electron transfer (MCET) vs.
1
17
118
metal ionꢀdecoupled electron transfer (MDET) or diimines with Lewis acids.
Scheme 2
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3. Conclusions
A novel mixedꢀligand oxidovanadium(IV) complex [VOCl
2
(dppꢀbian)] (1) with a squareꢀpyramidal
coordination environment of vanadium has been synthesized and fully characterized. This is a first
example of oxidovanadium complex containing bis(arylimino)acenaphthylene type ligand. The complex
ꢀ/⋅
ꢀ
is redox active and exhibits two quasiꢀreversible reduction processes assigned to the bian/bian and bian
/⋅/
static magnetic susceptibility measurements. The complex demonstrates high catalytic activity towards
alkanes oxygenation by H under mild conditions. The oxygenation is more efficient in the presence of
pyrazineꢀ2ꢀcarboxylic acid. We assume that the activation of H O toward homolysis occurs upon
bian couples. Paramagnetic d configuration of vanadium in 1 was supported by EPR spectroscopy and
2ꢀ
1
2
O
2
2
2
coordination of hydrogen peroxide to the metal center of the catalyst molecule and does not require the
change of the metal oxidation state and formation of the HOO• radical. A potentially substitutional
lability of chloride in 1 makes it a very attractive building block for construction of higher nuclearity
vanadium complexes in the presence of suitable bridging ligands or heterometallic systems.
4. Experimental section
4
.1 General procedures
All manipulations were carried out in air. VCl
diisopropylphenyl)imino]acenaphthene (dppꢀbian) was synthesized according to the published
3
was commercially available. Bis[Nꢀ(2,6ꢀ
119
procedure . All solvents were distilled by standard methods before use.
4.2 Physical Measurements
Elemental C, H, N analyses were performed with a EuroEA3000 Eurovector analyzer. IR spectra were
–1
recorded in the 4000–400 cm range with a Perkin–Elmer System 2000 FTIR spectrometer with samples
in KBr pellets. The cyclic voltammograms (CV) were recorded with a 797 VA Computrace system
(
Metrohm, Switzerland). All measurements were performed with a conventional threeꢀelectrode
configuration consisting of glassy carbon working and platinum auxiliary electrodes and an Ag/AgCl/KCl
reference electrode. The solvent used in all experiments was CH Cl which was deoxygenated before use.
Tetraꢀnꢀbutylammonium hexafluorophosphate (0.1 M solution) was used as a supporting electrolyte. The
2
2
ꢀ3
concentration of the complex was approximately 10 М. The redox potential values (E1/2) were
determined as (E + E )/2, where E and E are anodic and cathodic peak potentials, respectively. EPR
a
c
a
c
measurements were carried out at Xꢀband (9 GHz) using the commercial spectrometer Bruker Elexsys
E580. Modulation amplitude was 0.1 mT, mw frequency was ~9.7 GHz, mw power ~0.2 ꢀ 0.002 mW was
chosen to avoid saturation of spectral lines. Theoretical modeling of EPR spectra was performed using
1
20
EasySpin toolbox (Version 5.2.11) for Matlab . For characterization of complex 1 in solution it was
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ꢀ3
dissolved in toluene in concentration 10 M. All measurements were done with external reference DPPH
standard (2,2ꢀdiphenylꢀ1ꢀpicrylhydrazyl) for correct determination of g–tensor values. Static magnetic
susceptibility measurements of the polycrystalline sample were performed with a Quantum Design
MPMSXL SQUID magnetometer in the temperature range 2ꢀ300 K with magnetic field of up to 5 kOe.
Diamagnetic corrections were made using the Pascal constants. The effective magnetic moment was
2
1/2
1/2
calculated as µeff(T) = [(3k/N
A
µ
B
)χ
T]
≈ (8χT) .
4
.3. Xꢀray data collection and structure refinement
Crystallographic data and refinement details for 1·1.7CH
were collected on a New Xcalibur (Agilent Technologies) diffractometer with MoK radiation (λ =
2 2
Cl are given in Table 1. The diffraction data
α
0
.71073) by doing φ scans of narrow (0.5°) frames at 130 K. Absorption correction was done empirically
using SCALE3 ABSPACK (CrysAlisPro, Agilent Technologies, Version 1.171.37.35 (release 13ꢀ08ꢀ
014 CrysAlis171 .NET)). The structure of 1·1.7CH Cl was solved as inversion twin in Pc space group
2
2
2
2
(
BASF 0.57) by direct method and refined by fullꢀmatrix leastꢀsquares treatment against |F| in
1
21
122
anisotropic approximation with SHELX 2017/1 in ShelXle program . Hydrogen atoms were refined
in geometrically calculated positions. The main geometrical parameters are summarized in Table 2. The
crystallographic data have been deposed in the Cambridge Crystallographic Data Centre under the
deposition codes CCDC 1851928.
2 2
Table 1. Summary of the crystal data for compound 1·1.7CH Cl
Parameter
Chemical formula
Mr
2 2
1·1.7CH Cl
C
37.70 2
H43.40Cl5.40N OV
782.91
Crystal system, space Monoclinic, Pc
group
Temperature (K)
a, b, c (Å)
β (°)
130
11.5919 (2), 29.7642 (5), 12.0184 (2)
105.714 (2)
3991.65 (12)
4
3
V (Å )
Z
Radiation type
Mo Ka
ꢀ1
µ (mm )
0.64
Crystal size (mm)
Diffractometer
0.17 × 0.15 × 0.12
New Xcalibur, AtlasS2
Multiꢀscan
Absorption
correction
CrysAlis PRO 1.171.38.41 (Rigaku Oxford Diffraction,
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2015) Empirical absorption correction using spherical
harmonics, implemented in SCALE3 ABSPACK scaling
algorithm.
T , T
0.976, 1.000
min
max
No. of measured,
independent and
observed [I > 2σ(I)]
reflections
25845, 14630, 11553
R
int
0.019
θ values (°)
sin θ/λ)max (Å )
Range of h, k, l
θmax = 31.0, θmin = 3.3
0.724
ꢀ1
(
ꢀ15 ≤ h ≤ 14, ꢀ40 ≤ k ≤ 41, ꢀ17 ≤ l ≤ 13
0.072, 0.231, 1.05
2
2
R[F > 2σ(F )],
2
wR(F ), S
No. of reflections,
14630, 866, 32
parameters, restraints
Hꢀatom treatment
Weighting scheme
Hꢀatom parameters constrained
2
2
2
o
w = 1/[σ (F ) + (0.1417P) + 6.6061P]
2
2
o c
where P = (F + 2F )/3
ꢀ3
ꢂρmax, ꢂρmin (e Å ) 2.36, ꢀ0.99
Table 2. Selected bond distances (Å)* for compound 1·1.7CH Cl2
2
VꢀO
VꢀN
VꢀCl
CꢀN
CꢀC
1
1
.587 (8)
.567 (7)
2.176 (8)
2.154 (8)
2.279 (3)
2.287 (3)
2.295 (3)
2.288 (3)
1.303 (13)
1.302 (11)
1.257 (12)
1.273 (12)
1.501(13)
1.516(12)
2
.158 (8)
.136 (9)
2
*Standard deviations are given in brackets
4
.4. Synthesis of [VOCl
2
(dppꢀbian)] (1)
A mixture of VCl
3
(80 mg, 0.5 mmol) and dppꢀbian (255 mg, 0.5 mmol) in acetonitrile (15 ml) was
refluxed for 4 hours. The color of the solution changed from orange to brown. The reaction mixture was
evaporated to dryness, redissolved in CH Cl (7 ml). An excess of hexane was layered to the
dichloromethane solution resulting in brown crystals. Yield of brown crystals: 150 mg (50%). Anal. Calc.
2
2
−
1
for C36
H40Cl
2
N
2
OV: C, 67.7; N, 4.4; H, 6.3%. Found: C, 67.3; N, 4.3; H, 6.0%. IR (KBr) ν/cm : 3631
(br.w), 3438(br.w), 3249(w), 3166(w), 3061(br.w), 2964(br.vs), 2928(m), 2869(m), 1641(m), 1625(vs),
1
1
595(s), 1583(vs), 1489(w), 1464(m), 1437(m), 1420(m), 1385(m), 1364(m), 1325(w), 1294(m),
269(w), 1254(w), 1224(w), 1184(br.w), 1130(w), 1112(w), 1089(w), 1054(br.w), 1008(s), 997(s),
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4
57(w), 937(w), 852(w), 837(m), 800(m), 782(s), 758(vs), 733(m), 702(w), 617(w), 577(w), 543(w),
ꢀ1
ꢀ1
72(w), 409(m). UVꢀvis (CH
Cl , vs. Ag/AgCl): oxidation – Ea = +1.40 V; reduction – E1/2 = ꢀ0.32 V (
E = 0.23 V), Ec = ꢀ1.6 V at a potential sweep rate of 0.1 V/s.
2
Cl
2
) λmax/nm (ε/M cm ): 275 (54 330), 330 (15390), 495 (1840). CV
(CH
2
2
ꢁ
E = 0.10 V), E1/2 = ꢀ1.05
V (
ꢁ
3
4
.5. Alkane oxygenation reactions
Aliquots of solutions of catalyst 1 and coꢀcatalyst (PCA) were added to the reaction mixtures in alkane
oxidation. The reactions of alkanes with H (50% aqueous) were typically carried out in air in
thermostated Pyrex cylindrical vessels with vigorous stirring (CAUTION: the combination of air or
molecular oxygen and H with organic compounds at elevated temperatures may be explosive!). The
reactions were stopped by cooling, and typically analyzed twice, i.e., before and after the addition of an
2
O
2
2
O
2
41,94,95,97–101,123,124
excess of solid PPh
3
. This method was developed previously by one of us
for the
analysis of reaction mixtures obtained from various alkane oxidations. In the case of the formation of the
corresponding alkyl hydroperoxides as the main products, if an excess of solid PPh is added to a sample
3
of the reaction solution, ca. 10 min before GC analysis, the alkyl hydroperoxide present is completely
reduced to the corresponding alcohol. As a result, the chromatogram differs from that of a sample not
subjected to the reduction: the alcohol peak rises, while the intensity of the ketone peak decreases. In our
kinetic studies for precise determination of oxygenate concentrations only data obtained after reduction of
3
the reaction sample with PPh were used. The chromatographꢀ3700 (fused silica capillary column
FFAP/OVꢀ101 20/80 w/w, 30 m × 0.2 mm × 0.3 µm; helium as a carrier gas was employed. Attribution
of peaks was made by comparison with chromatograms of authentic samples. Blank experiments with
cyclohexane showed that in the absence of catalyst 1 no products were formed. Typical chromatograms
obtained for the mixtures of products from nꢀheptane and methylcyclohexane oxidations are shown in
Figs. S2 and S3, respectively.
Conflict of interest
The authors declare no financial interest.
Acknowledgements
We thank Federal Agency for Scientific Organizations and Russian Foundation for Basic Research
(
grants Nos. 16ꢀ03ꢀ00254 and 18ꢀ03ꢀ00155ꢀа) for funding. A. S. P. and A. M. S. also thank FASO Russia
project 0333ꢀ2016ꢀ0001).
(
References
1
W. Kaim, Inorg. Chem., 2011, 50, 9752–9765.
17

New Journal of Chemistry
Page 18 of 24
View Article Online
DOI: 10.1039/C8NJ03358G
2
3
4
5
6
W. Kaim, Coord. Chem. Rev., 1987, 76, 187–235.
V. Lyaskovskyy and B. De Bruin, ACS Catal., 2012, 2, 270–279.
P. J. Chirik and K. Wieghardt, Science (80ꢀ. )., 2010, 327, 794–795.
A. F. Heyduk, R. A. Zarkesh and A. I. Nguyen, Inorg. Chem., 2011, 50, 9849–9863.
V. K. K. Praneeth, M. R. Ringenberg, T. R. Ward, O. R. Luca, R. H. Crabtree, V. K. K. Praneeth,
M. R. Ringenberg and T. R. Ward, Chem. Soc. Rev., 2012, 51, 10228–10234.
D. D. Wright and S. N. Brown, Inorg. Chem., 2013, 52, 7831–3.
7
8
Y. S. Fomenko, A. L. Gushchin, V. A. Nadolinny, P. A. Abramov and M. N. Sokolov, J. Struct.
Chem., 2017, 58, 964–969.
9
1
1
J. A. Stubbe and W. A. Van Der Donk, Chem. Rev., 1998, 98, 705–762.
W. Kaim and B. Schwederski, Coord. Chem. Rev., 2010, 254, 1580–1588.
M. Villa, D. Miesel, A. Hildebrandt, F. Ragaini, D. Schaarschmidt and A. Jacobi von Wangelin,
ChemCatChem, 2017, 9, 3203–3209.
0
1
12
A. Scarel, M. R. Axet, F. Amoroso, F. Ragaini, C. J. Elsevier, A. Holuigue, C. Carfagna, L. Mosca
and B. Milani, Organometallics, 2008, 27, 1486–1494.
13
14
15
16
17
F. Ragaini, S. Cenini and M. Gasperini, J. Mol. Catal. A Chem., 2001, 174, 51–57.
D. B. Llewellyn, D. Adamson and B. A. Arndtsen, Org. Lett., 2000, 2, 4165–4168.
D. H. Leung, J. W. Ziller and Z. Guan, J. Am. Chem. Soc., 2008, 130, 7538–7539.
Jeffrey M. Rose, A. Anna E. Cherian and G. W. Coates, J. Am. Chem. Soc., 2006, 128, 4186–4187.
D. J. Tempel, L. K. Johnson, R. Leigh Huff, P. S. White and M. Brookhart, J. Am. Chem. Soc.,
2000, 122, 6686–6700.
18
19
20
L. Li, C. S. B. Gomes, P. T. Gomes, M. T. Duarte and Z. Fan, Dalt. Trans., 2011, 40, 3365.
J. Flapper and J. N. H. Reek, Angew. Chemie Int. Ed., 2007, 46, 8590–8592.
A. E. Cherian, J. M. Rose, E. B. Lobkovsky and G. W. Coates, J. Am. Chem. Soc., 2005, 127,
13770–13771.
21
22
23
24
F. Amoroso, E. Zangrando, C. Carfagna, C. Müller, D. Vogt, M. Hagar, F. Ragaini and B. Milani,
Dalt. Trans., 2013, 42, 14583.
C. Romain, V. Rosa, C. Fliedel, F. Bier, F. Hild, R. Welter, S. Dagorne and T. Avilés, Dalt. Trans.,
2012, 41, 3377.
A. L. Gottumukkala, J. F. Teichert, D. Heijnen, N. Eisink, S. van Dijk, C. Ferrer, A. van den
Hoogenband and A. J. Minnaard, J. Org. Chem., 2011, 76, 3498–3501.
B. Scott Williams, Mark D. Leatherman, P. S. White and M. Brookhart, J. Am. Chem. Soc., 2005,
127, 5132–5146.
2
5
6
L. K. Johnson, C. M. Killian and M. Brookhart, J. Am. Chem. Soc., 1995, 117, 6414–6415.
2
L. Li, P. S. Lopes, V. Rosa, C. A. Figueira, M. A. N. D. A. Lemos, M. T. Duarte, T. Avilés and P.
18

Page 19 of 24
New Journal of Chemistry
View Article Online
DOI: 10.1039/C8NJ03358G
T. Gomes, Dalt. Trans., 2012, 41, 5144–5154.
2
7
8
M. Viganò, F. Ragaini, M. G. Buonomenna, R. Lariccia, A. Caselli, E. Gallo, S. Cenini, J. C.
Jansen and E. Drioli, ChemCatChem, 2010, 2, 1150–1164.
2
I. L. Fedushkin, M. V. Moskalev, A. N. Lukoyanov, A. N. Tishkina, E. V. Baranov and G. A.
Abakumov, Chem. ꢀ A Eur. J., 2012, 18, 11264–11276.
2
9
0
M. Gholinejad, V. Karimkhani and I. Kim, Appl. Organomet. Chem., 2014, 28, 221–224.
C. D. Nunes, P. D. Vaz, V. Félix, L. F. Veiros, T. Moniz, M. Rangel, S. Realista, A. C. Mourato
and M. J. Calhorda, Dalt. Trans., 2015, 44, 5125–5138.
3
31
L. Li, P. S. Lopes, C. A. Figueira, C. S. B. Gomes, M. T. Duarte, V. Rosa, C. Fliedel, T. Avilés and
P. T. Gomes, Eur. J. Inorg. Chem., 2013, 2013, 1404–1417.
3
3
3
2
3
4
M. W. van Laren and C. J. Elsevier, Angew. Chemie Int. Ed., 1999, 38, 3715–3717.
J. Bendix and K. M. Clark, Angew. Chemie Int. Ed., 2016, 55, 2748–2752.
I. L. Fedushkin, D. S. Yambulatov, A. A. Skatova, E. V. Baranov, S. Demeshko, A. S.
Bogomyakov, V. I. Ovcharenko and E. M. Zueva, Inorg. Chem., 2017, 56, 9825–9833.
I. L. Fedushkin, O. V. Maslova, E. V. Baranov and A. S. Shavyrin, Inorg. Chem., 2009, 48, 2355–
35
36
37
2357.
I. L. Fedushkin, O. V. Maslova, A. G. Morozov, S. Dechert, S. Demeshko and F. Meyer, Angew.
Chemie Int. Ed., 2012, 51, 10584–10587.
A. E. Shilov and G. B. Shul’pin, Activation and Catalytic Reactions of Saturated Hydrocarbons in
the Presence ... ꢀ A.E. Shilov, Georgiy B. Shul’pin ꢀ Google Книги, New York, Boston, Dordrecht,
London, Moscow, 2002.
3
8
9
E. T. Denisov and I. B. Afanas’ev, Oxidation and Antioxidants in Organic Chemistry and Biology ꢀ
Evgeny T. Denisov, Igor B. Afanas’ev ꢀ Google Books, 2005.
3
G. B. Shul’pin, in Comprehensive Inorganic Chemistry II, 2nd Edition, eds. J. Reedijk, K.
Poeppelmeier and L. Casella, Elsevier, 2013, pp. 79–104.
40
41
42
H. WójtowiczꢀMłochowska, Arkivoc, 2017, 12–58.
G. Shul’pin and G. B., Catalysts, 2016, 6, 50.
S. RachmilovichꢀCalis, A. Masarwa, N. Meyerstein, D. Meyerstein and R. van Eldik, Chem. ꢀ A
Eur. J., 2009, 15, 8303–8309.
43
44
45
46
47
48
A. S. Petit, R. C. R. Pennifold and J. N. Harvey, Inorg. Chem., 2014, 53, 6473–6481.
Q. Zhang and C. R. Goldsmith, Inorg. Chem., 2014, 53, 5206–5211.
G. B. Shul’pin, Dalt. Trans., 2013, 42, 12794.
D. C. Crans, Jason J. Smee, E. Gaidamauskas and L. Yang, Chem. Rev., 2004, 104, 849–902.
D. C. Crans, B. Baruah, A. Ross and N. E. Levinger, Coord. Chem. Rev., 2009, 253, 2178–2185.
M. Aureliano and D. C. Crans, J. Inorg. Biochem., 2009, 103, 536–546.
19

New Journal of Chemistry
Page 20 of 24
View Article Online
DOI: 10.1039/C8NJ03358G
49
50
51
M. J. Pereira, E. Carvalho, J. W. Eriksson, D. C. Crans and M. Aureliano, J. Inorg. Biochem.,
009, 103, 1687–1692.
D. C. Crans, A. M. Trujillo, P. S. Pharazyn and M. D. Cohen, Coord. Chem. Rev., 2011, 255,
178–2192.
2
2
A. S. Tracey, G. R. Willsky and E. S. Takeuchi, Vanadium: Chemistry, Biochemistry,
Pharmacology and Practical Applications, Boca Raton, 2007.
5
5
5
5
5
2
3
4
5
6
D. Rehder, Bioinorganic vanadium chemistry, John Wiley & Sons, 2008.
A. Butler, M. J. Clague and G. E. Meister, Chem. Rev., 1994, 94, 625–638.
C. Bolm, Coord. Chem. Rev., 2003, 237, 245–256.
J.ꢀM. Brégeault, Dalt. Trans., 2003, 0, 3289–3302.
J.ꢀM. Brégeault, M. Vennat, Laurent Salles, J.ꢀY. Piquemal, Y. Mahha, E. Briot, P. C. Bakala, A.
Atlamsani and R. Thouvenot, J. Mol. Catal. A Chem., 2006, 250, 177–189.
J. A. L. da Silva, J. J. R. F. da Silva and A. J. L. Pombeiro, Coord. Chem. Rev., 2011, 255, 2232–
5
7
8
2248.
5
M. Sutradhar, L. M. D. R. S. Martins, M. F. C. Guedes da Silva and A. J. L. Pombeiro, Coord.
Chem. Rev., 2015, 301–302, 200–239.
5
9
0
K. Kustin, J. C. Pessoa and D. C. Crans, Vanadium: the Versatile Metal, ACS Sympos., 2007.
I. Gryca, K. Czerwińska, B. Machura, A. Chrobok, L. S. Shul’pina, M. L. Kuznetsov, D. S.
Nesterov, Y. N. Kozlov, A. J. L. Pombeiro, I. A. Varyan and G. B. Shul’pin, Inorg. Chem., 2018,
6
57, 1824–1839.
6
1
2
M. Sutradhar, N. V. Shvydkiy, M. F. C. Guedes da Silva, M. V. Kirillova, Y. N. Kozlov, A. J. L.
Pombeiro and G. B. Shul’pin, Dalt. Trans., 2013, 42, 11791–11803.
6
G. SüssꢀFink, G. V Nizova, S. Stanislas and G. B. Shul’pin, J. Mol. Catal. A Chem., 1998, 130,
163–170.
63
64
65
66
67
68
69
70
G. V Nizova, G. SüssꢀFink and G. B. Shul’pin, Tetrahedron, 1997, 53, 3603–3614.
G. V. Nizova, G. SüssꢀFink and G. B. Shul’pin, Chem. Commun., 1997, 0, 397–398.
G. B. Shul’pin, M. C. Guerreiro and U. Schuchardt, Tetrahedron, 1996, 52, 13051–13062.
G. B. Shul’pin, R. S. Drago and M. Gonzalez, Russ. Chem. Bull., 1996, 45, 2386–2388.
G. B. Shul’pin, A. N. Druzhinina and G. V. Nizova, Russ. Chem. Bull., 1993, 42, 1326–1329.
G. B. Shulpin, D. Attanasio and L. Suber, J. Catal., 1993, 142, 147–152.
G. B. Shul’pin, D. Attanasio and L. Suber, Russ. Chem. Bull., 1993, 42, 55–59.
G. B. Shul’pin, Y. N. Kozlov, G. V. Nizova, G. SüssꢀFink, S. Stanislas, A. Kitaygorodskiy and V.
S. Kulikova, J. Chem. Soc. Perkin Trans. 2, 2001, 1351–1371.
7
1
2
A. M. Kirillov and G. B. Shul’pin, Coord. Chem. Rev., 2013, 257, 732–754.
7
M. V. Kirillova, M. L. Kuznetsov, V. B. Romakh, L. S. Shul’pina, J. J. R. Fraústo da Silva, A. J. L.
20

Page 21 of 24
New Journal of Chemistry
View Article Online
DOI: 10.1039/C8NJ03358G
Pombeiro and G. B. Shul’pin, J. Catal., 2009, 267, 140–157.
7
3
4
E. V. Gusevskaya, L. Menini, L. A. Parreira, R. A. Mesquita, Y. N. Kozlov and G. B. Shul’pin, J.
Mol. Catal. A Chem., 2012, 363–364, 140–147.
7
Y. N. Kozlov, V. B. Romakh, A. Kitaygorodskiy, P. Buglyó, G. SüssꢀFink and G. B. Shul’pin, J.
Phys. Chem. A, 2007, 111, 7736–7752.
7
5
6
R. Z. Khaliullin, A. T. Bell and M. HeadꢀGordon, J. Phys. Chem. B, 2005, 109, 17984–17992.
M. H. C. de la Cruz, Y. N. Kozlov, E. R. Lachter and G. B. Shul’pin, New J. Chem., 2003, 27,
7
634–638.
77
78
79
G. B. Shul’pin and E. R. Lachter, J. Mol. Catal. A Chem., 2003, 197, 65–71.
G. B. Shul’pin, Y. Ishii, S. Sakaguchi and T. Iwahama, Russ. Chem. Bull., 1999, 48, 887–890.
Y. S. Fomenko, A. L. Gushchin, A. V. Tkachev, E. S. Vasilyev, P. A. Abramov, V. A. Nadolinny,
M. M. Syrokvashin and M. N. Sokolov, Polyhedron, 2017, 135, 96–100.
80
81
82
J. A. Bonadies and C. J. Carrano, J. Am. Chem. Soc., 1986, 108, 4088–4095.
X. Li, M. S. Lah and V. L. Pecoraro, Inorg. Chem., 1988, 27, 4657–4664.
E. KimeꢀHunt, K. Spartalian, M. DeRusha, C. M. Nunn and C. J. Carrano, Inorg. Chem., 1989, 28,
4392–4399.
83
84
85
86
P. B. Hitchcock, T. H. Lee and G. . Leigh, Inorganica Chim. Acta, 2003, 349, 159–164.
C. Lorber and L. Vendier, Dalt. Trans., 2009, 6972.
W. A. Nugent and J. M. Mayer, MetalꢀLigand Multiple Bonds, New York, 1988.
M. Viganò, F. Ferretti, A. Caselli, F. Ragaini, M. Rossi, P. Mussini and P. Macchi, Chem. ꢀ A Eur.
J., 2014, 20, 14451–14464.
87
88
89
90
N. Muresan, C. C. Lu, M. Ghosh, J. C. Peters, M. Abe, L. M. Henling, T. Weyhermöller, E. Bill
and K. Wieghardt, Inorg. Chem., 2008, 47, 4579–4590.
P. A. Abramov, A. A. Dmitriev, K. V. Kholin, N. P. Gritsan, M. K. Kadirov, A. L. Gushchin and
M. N. Sokolov, Electrochim. Acta, 2018, 270, 526–534.
I. L. Fedushkin, A. A. Skatova, V. A. Chudakova and G. K. Fukin, Angew. Chemie Int. Ed., 2003,
42, 3294–3298.
I. L. Fedushkin, V. A. Dodonov, A. A. Skatova, V. G. Sokolov, A. V. Piskunov and G. K. Fukin,
Chem. ꢀ A Eur. J., 2018, 24, 1877–1889.
9
9
9
1
2
3
K. Hasan and E. ZysmanꢀColman, J. Phys. Org. Chem., 2013, 26, 274–279.
P. Galloni, A. Coletti, B. Floris and V. Conte, Inorganica Chim. Acta, 2014, 420, 144–148.
A. Apostolopoulou, M. Vlasiou, P. A. Tziouris, C. Tsiafoulis, A. C. Tsipis, D. Rehder, T. A.
Kabanos, A. D. Keramidas and E. Stathatos, Inorg. Chem., 2015, 54, 3979–3988.
G. Olivo, O. Lanzalunga and S. Di Stefano, Adv. Synth. Catal., 2016, 358, 843–863.
I. GarciaꢀBosch and M. A. Siegler, Angew. Chemie, 2016, 128, 13065–13068.
9
4
5
9
21

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DOI: 10.1039/C8NJ03358G
9
6
7
G. B. Shul’pin, Org. Biomol. Chem., 2010, 8, 4217.
9
G. B. Shul’pin, Y. N. Kozlov, L. S. Shul’pina and P. V. Petrovskiy, Appl. Organomet. Chem.,
010, 24, 464–472.
G. B. Shul’pin, Y. N. Kozlov, L. S. Shul’pina, A. R. Kudinov and D. Mandelli, Inorg. Chem.,
009, 48, 10480–10482.
G. Shul’pin, Mini. Rev. Org. Chem., 2009, 6, 95–104.
2
98
2
9
1
1
1
1
9
00 G. B. Shul’pin, Comptes Rendus Chim., 2003, 6, 163–178.
01 G. B. Shul’pin, J. Mol. Catal. A Chem., 2002, 189, 39–66.
02 G. B. Shulpin and A. N. Druzhinina, React. Kinet. Catal. Lett., 1992, 47, 207–211.
03 D. S. Nesterov, E. N. Chygorin, V. N. Kokozay, V. V. Bon, R. Boča, Y. N. Kozlov, L. S.
Shul’pina, J. Jezierska, A. Ozarowski, A. J. L. Pombeiro and G. B. Shul’pin, Inorg. Chem., 2012,
51, 9110–9122.
1
04 G. B. Shul’pin, D. S. Nesterov and L. S. Shul’pina, Inorganica Chim. Acta, 2017, 455, 666–676.
05 M. M. Vinogradov, Y. N. Kozlov, D. S. Nesterov, L. S. Shul’pina, A. J. L. Pombeiro and G. B.
Shul’pin, Catal. Sci. Technol., 2014, 4, 3214–3226.
1
106 M. M. Vinogradov, Y. N. Kozlov, A. N. Bilyachenko, D. S. Nesterov, L. S. Shul’pina, Y. V.
Zubavichus, A. J. L. Pombeiro, M. M. Levitsky, A. I. Yalymov and G. B. Shul’pin, New J. Chem.,
2015, 39, 187–199.
1
07 L. S. Shul’pina, A. R. Kudinov, D. Mandelli, W. A. Carvalho, Y. N. Kozlov, M. M. Vinogradov,
N. S. Ikonnikov and G. B. Shul’pin, J. Organomet. Chem., 2015, 793, 217–231.
08 G. Tanarungsun, W. Kiatkittipong, S. Assabumrungrat, H. Yamada, T. Tagawa and P.
Praserthdam, J. Ind. Eng. Chem, 2007, 13, 444–451.
1
1
09 L. Zhu and C. Hu, in Ionic Liquids ꢀ New Aspects for the Future, InTech, 2013.
10 X. Hu, L. Zhu, X. Wang, B. Guo, J. Xu, G. Li and C. Hu, J. Mol. Catal. A Chem., 2011, 342–343,
1
41–49.
111 M. P. DeMatteo, J. S. Poole, X. Shi, R. Sachdeva, P. G. Hatcher, C. M. Hadad and M. S. Platz, J.
Am. Chem. Soc., 2005, 127, 7094–7109.
112 S. Yamaguchi, T. Ohnishi, Y. Miyake and H. Yahiro, Chem. Lett., 2015, 44, 1287–1288.
113 V. B. Romakh, B. Therrien, G. SüssꢀFink and G. B. Shul’pin, Inorg. Chem., 2007, 46, 1315–1331.
114 B. G. M. Rocha, M. L. Kuznetsov, Y. N. Kozlov, A. J. L. Pombeiro and G. B. Shul’pin, Catal. Sci.
Technol., 2015, 5, 2174–2187.
1
1
15 M. L. Kuznetsov, F. A. Teixeira, N. A. Bokach, A. J. L. Pombeiro and G. B. Shul’pin, J. Catal.,
2
014, 313, 135–148.
16 A. S. Novikov, M. L. Kuznetsov, A. J. L. Pombeiro, N. A. Bokach and G. B. Shul’pin, ACS Catal.,
013, 3, 1195–1208.
2
22

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New Journal of Chemistry
View Article Online
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117 S. Fukuzumi and K. Ohkubo, Coord. Chem. Rev., 2010, 254, 372–385.
1
18 G. A. Abakumov, V. K. Cherkasov, A. V. Piskunov, O. Y. Trofimova and G. V. Romanenko,
Dokl. Chem., 2010, 434, 237–240.
119 A. Paulovicova, U. ElꢀAyaan, K. Shibayama, T. Morita and Y. Fukuda, Eur. J. Inorg. Chem.,
2001, 2001, 2641–2646.
1
1
1
1
1
20 S. Stoll and A. Schweiger, J. Magn. Reson., 2006, 178, 42–55.
21 G. M. Sheldrick and IUCr, Acta Crystallogr. Sect. C Struct. Chem., 2015, 71, 3–8.
22 C. B. Hübschle, G. M. Sheldrick and B. Dittrich, J. Appl. Crystallogr., 2011, 44, 1281–1284.
23 G. B. Shul’pin, Org. Biomol. Chem., 2010, 8, 4217.
24 G. B. Shulpin and A. N. Druzhinina, React. Kinet. Catal. Lett., 1992, 47, 207–211.
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Graphical Abstract:
Text for Graphical Abstract:
The combination of a new oxovanadium(IV) complex 1 with pyrazineꢀ2ꢀcarboxylic acid (PCA; a
cocatalyst) affords a catalytic system for the efficient oxidation of saturated hydrocarbons with hydrogen
peroxide to produce alkyl hydroperoxides.
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