Copper(I) and copper(II) metallacycles as catalysts for microwave assisted selective oxidation of cyclohexane

Article abstract of DOI:10.1016/j.poly.2017.06.020

New copper(I) and copper(II) pyrazolate compounds have been prepared by similar synthesis procedures. For the 3,5-NO₂-pyrazole ligands, the dinuclear cyclic Cu(I) compound [Cu₂(μ-N,N-3,5-(NO₂)₂pz)₂(PP

Full text of DOI:10.1016/j.poly.2017.06.020

Accepted Manuscript
Copper(I) and copper(II) metallacycles as catalysts for microwave assisted se-
lective oxidation of cyclohexane
Rossana Galassi, Oumarou Camille Simon, Alfredo Burini, Giorgio Tosi, Carla
Conti, Claudia Graiff, Nuno M.R. Martins, M. Fátima C. Guedes da Silva,
Armando J.L. Pombeiro, Luísa M.D.R.S. Martins
PII:
S0277-5387(17)30438-2
DOI:
http://dx.doi.org/10.1016/j.poly.2017.06.020
POLY 12701
Reference:
Polyhedron
To appear in:
Received Date:
Revised Date:
Accepted Date:
20 April 2017
30 May 2017
2 June 2017
Please cite this article as: R. Galassi, O.C. Simon, A. Burini, G. Tosi, C. Conti, C. Graiff, N.M.R. Martins, M.F.C.
Guedes da Silva, A.J.L. Pombeiro, L.M.D. Martins, Copper(I) and copper(II) metallacycles as catalysts for
microwave assisted selective oxidation of cyclohexane, Polyhedron (2017), doi: http://dx.doi.org/10.1016/j.poly.
2017.06.020
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

COPPER(I) AND COPPER(II) METALLACYCLES AS CATALYSTS FOR MICROWAVE
ASSISTED SELECTIVE OXIDATION OF CYCLOHEXANE
Rossana Galassi*[a], Oumarou Camille Simon[a], Alfredo Burini[a], Giorgio Tosi[b], Carla Conti[b],
Claudia Graiff[c], Nuno M. R. Martins[d], M. Fátima C. Guedes da Silva[d], Armando J. L. Pombeiro[d],
Luísa M. D. R. S. Martins*[d],[e]
[a]
School of Science and Technology, University of Camerino
Via Sant’Agostino,1, I-62032, Camerino, Italy. Email: rossana.galassi@unicam.it
[b]
[c]
[d]
[e]
Dipartimento di Scienze e Ingegneria della Materia, dell'Ambiente ed Urbanistica, Politecnica delle Marche, Via Brecce Bianche, I-60131, Ancona, Italy
Department of Chemistry, Università di Parma, Viale delle Scienze, 17/A 43100, Parma, Italy
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
Department Chemical Engineering, Instituto Superior de Engenharia de Lisboa, Instituto Politécnico de Lisboa, R. Conselheiro Emídio Navarro, 1959-007 Lisboa,
Portugal. Email: lmartins@deq.isel.ipl.pt
Supporting information for this article is given via a link at the end of the document.
Abstract: New copper(I) and copper(II) pyrazolate compounds have been prepared by similar
synthesis procedures. For the 3,5-NO2-pyrazole ligands, the dinuclear cyclic Cu(I) compound
[Cu2(µ-N,N-3,5-(NO2)2pz)2(PPh3)2], 1, was the only compound isolated in high yield, while in the
case of the 3,5-bis(trifluoromethyl)-pyrazole ligand a spontaneous rearrangement to the hexanuclear
cyclic [trans-Cu6(µ-OH)6(µ-3,5-(CF3)2pz)6], 2, was observed. The formation of this latter compound
ruled out an anion templating mechanism for the synthesis. X-ray diffraction analysis of 1 revealed
that the copper cation is in a trigonal environment and involved in a six-membered Cu2N4 core;
while the structural analysis of 2 showed that the metal adopts a square-planar geometry, forms
five-membered Cu2N2O rings and ultimately gives rise to a large Cu6(N2O)6 crown-type assembly.
Compounds 1 and 2 act as very effective homogeneous catalysts towards the neat microwave (MW)
assisted peroxidative (with aq. tert-butyl hydroperoxide, TBHP) oxidation of cyclohexane to
cyclohexanol and cyclohexanone (total yield up to 58% in 30 min reaction time) via formation of
cyclohexyl hydroperoxide (CyOOH) as the primary product.
Introduction
The coordination chemistry of polynuclear Cu(I) and Cu(II) compounds with N-donor ligands
provides a wide number of complexes which are relevant in many areas such as catalysis [1],
bioinorganic chemistry [2], materials chemistry [3] and molecular magnetism [4]. The above-
mentioned areas are strictly related to each other. In fact, copper(II) ions are active catalysts in the
oxidation of water to molecular oxygen [1] and copper(II) 1,10-phenanthroline complexes are
involved in the aerobic oxidation of primary alcohols; moreover, dinuclear copper(II) proteins, such
as hemocyanins, tyrosinase and catechol oxidase, activate molecular oxygen by a “side-on”
bridging binding mode [2b], providing different biological functions: the (oxygen transport, ortho-
hydroxylation of phenols with further oxidation of the cathecol product to o-quinone or the
enantioselective oxidation of DOPA, DihydrOxyPhenylAlanine) [1e]. It is clear that the enzymatic

catalysis of oxidations is largely based on cooperativity between the metal center and functional
organic ligands located in its surroundings. As a consequence, a strategy on the design of copper
based catalysts for oxidation reactions should consider a biomimetic approach [5]. The synthesis of
bioinspired copper pyrazolate metallacycles may proceed by spontaneous self-assembly of
deprotonated ligands and Cu(II) salts or Cu(I) oxide [6], by templating syntheses [7] or by
rearrangements of polynuclear copper(I) compounds to copper(II) derivatives [3c,8]. In the last
case, the reaction of a trinuclear Cu(I) metallacycle, depicted as [µ-Cu-N,N-3,5-pz(CF3)2]3, where
3,5-(CF3)2-pz is 3,5-bis(trifluoromethyl)pyrazolate, with a halide source such as [Bu4N]X or
PPNNO2 ([Bu4N] = tetrabutyl ammonium, PPN = phosphoranylamide, X = Cl, Br or I) or
Ph3PAuCl, led to the formation of anion encapsulated adducts in a 1:1 mole ratio [3c,4c] The X-ray
diffraction analyses revealed for all these compounds a core containing a hexanuclear copper(II)
ring bridged by six hydroxyl groups and six pyrazolate ligands. The mechanism leading to the
Cu6O6N6 metal framework is not very clear and it was hypothesized that the anions could template
the formation of the hexanuclear cycle.
The first aim of this work was to investigate the mechanism leading to the synthesis of such
complexes. Moreover, to center this target, the synthesis has been extended to a similar pyrazolate
ligand, having nitro groups in the 3,5 positions. Further, the catalytic activity of the obtained
compounds towards the peroxidative oxidation of cyclohexane was tested. This reaction was
selected as an alkane oxidation model due to its industrial and economical importance, in view of
the significance of the oxidized products (cyclohexanol and cyclohexanone) for the manufacture of
adipic acid and caprolactam (precursors to Nylon-6,6 and polyamides). Moreover, the current
industrial process for cyclohexane oxidation requires 15 bar O2, 160 ºC and leads to very low
conversions (ca. 4%) to assure a reasonable selectivity (ca. 85%) [9]. Therefore, there is an urgent
need to design selective and effective catalytic processes for cyclohexane oxidation under mild and
solvent-free conditions, with environmentally benign oxidants [10] and, in this respect, a promising
approach is presented herein.
Results and discussion
Syntheses. A general method for the formation of pyrazolate copper metallocycles proceeds by
-
pyrazole deprotonation (by a base such as OH-, O2 , H-, etc.) and the reaction with metal ion sources
(i.e. Cu(I) halides, [Cu(CH3CN)4]BF4, Cu2O, etc.). In the case of 3,5-dinitro-pyrazole, the syntheses
were attempted with the aim to obtain trinuclear and/or hexanuclear compounds according to the
already reported reaction methods [3c,4c,6a,6b], though neither the trinuclear nor the hexanuclear
complexes were obtained. This pyrazole holds withdrawing groups in the 3,5 positions, but the

stronger withdrawing power of the nitro groups with respect to CF3 groups seems not to allow the
cyclization arrangement. On the other hand, the reaction of the 3,5-dinitropyrazole sodium salt with
Cu(BF4)2 in the presence of PPh3 affords the compound [Cu2(µ-N,N-3,5-(NO2)2pz)2(PPh3)2] 1, an
orange crystalline solid, the characterization of which showed two copper(I) centers bound to two
pyrazole ligands and to PPh3 co-ligands in a syn geometry, forming a cyclic dinuclear compound.
The phosphane had the function to reduce the Cu(II) ions to Cu(I) ions and to satisfy the
coordination requirements of the metal center, affording to a cycle where two pyrazole ligands
1
bridge the metal centers. ESI MS, VT H NMR, 31P NMR and X-ray diffraction analyses of 1
underline a pretty stable boat shaped hexa-membered N2Cu2N2 cycle with the phosphane ligand
bound to the metal centers, given the + 7 ppm shift from the that of free PPh3.
In the case of 3,5-(trifluoromethyl)pyrazole, the synthesis of the metallocyclic copper(II)
derivatives has already been reported and, as it concerns a hexanuclear compound, it consists of a
two step procedure [3c,4c]. The first step is the preparation of the trinuclear cyclic Cu(I) derivative
by starting from the neutral pyrazole, (CF3)2PzH, and Cu2O in an oxygen free environment,
followed by conversion of the Cu(I) trinuclear derivative to the hexanuclear complex upon
treatment with [Bu4N]X (X = Cl, Br or I) or PPNNO2 in wet acetonitrile and in the presence of air.
A synthetic mechanism through the template action of anions was proposed for these metallocycles
[4c]. In this regard, the direct reaction of 3,5-bis(trifluoromethyl)pyrazole, Cu2O and anion sources
in a 6:3:1 molar ratio yielded compounds 2a-d according to reaction Scheme 1.
F3C
CF3
CF3
F3C
N
N
O
Cu
Cu
CF3
H
N
N
O
O
N
Cu
N
N
3 Cu2O, wet MeCN, O2
F3C
H
H
H
H
CF3
CF3
N
6
Bu4N+
Cu
N
F3C
X-
Bu4NX ( X = Cl, Br, I)
PPNNO2
N
F3C
O
O
H
N
N
H
Cu
Cu
O
N
N
CF3
CF3
CF3
F3C

Scheme 1. Reaction scheme for the direct synthesis of compounds 2a-d with different anions
starting from the neutral 3,5-(CF3)2-pyrazole ligand.
1
Compounds 2a-d were characterized by elemental analysis, H and 19F NMR, IR, UV-visible
spectroscopy and ESI MS spectrometry, and the data obtained were compared to those previously
reported [3c]. This direct reaction was then repeated in the absence of any anion source, both
starting from [Cu-µ-3,5(CF3)2pz)]3 and from the bare 3,5(CF3)2pz-1H and Cu2O (Scheme 2). In
both reactions, the hydrated hexanuclear metallacycle 2 was obtained.
F3C
CF3
CF3
F3C
N
N
CF3
O
F3C
Cu
Cu
N
H
N
O
O
N
Cu
N
Cu
N
N
N
F3C
H
H
H
H
CF3
CF3
wet MeCN, O2
N
a)
N
F3C
2
CF3
Cu
N
H2O
F3C
Cu
Cu
O
O
N
N
N
N
H
Cu
Cu
F3C
CF3
O
N
N
CF3
CF3
CF3
CF3
F3C
F3C
CF3
F3C
N
N
O
Cu
Cu
CF3
H
N
N
O
O
N
N
3 Cu2O, wet MeCN, O2
F3C
H
H
H
H
CF3
CF3
b)
N
6
Cu
N
Cu
N
F3C
H2O
N
F3C
O
H
O
N
N
H
Cu
Cu
O
N
N
CF3
CF3
CF3
F3C
Scheme 2. Reaction schemes for the formation of compound 2: a) starting from the trimer (yield
82%), b) starting from the bare neutral pyrazole (yield 45%).
Compound 2 is poorly soluble in acetonitrile. The elemental analysis confirms the presence of the
metallocycle, two molecules of CH3CN and one of water. It readily encapsulates halides and NO2-

anions when the corresponding anion source is added in a 1:1 molar ratio in acetonitrile or acetone
1
solutions. The H NMR characterization of 2 showed the C4-H signal of the pyrazole group at δ 25
ppm in acetone-d6 and δ 35 ppm in CD3CN, as already observed for the other anion centered
metallacycles 2a-d. The line width at half height of the δ 25 ppm signal is 36 Hz, while the water of
acetone falls at δ 3.93 ppm instead of the usual δ 2.8 ppm; these shifts suggest a likely water
exchange process between the “encapsulated” water molecules and the free water molecules of the
deuterated solvent. A VT NMR experiment (see Supporting Information) allowed the determination
of the exchange rate constant as 7.1 x 107 s-1 (-20 °C), typical of a fast exchange regime [11]. A
detailed solid state IR characterization of compounds 2 and 2a-d was also performed. The MIR
spectrum of 2 shows typical bands for the bridging hydroxyl groups, already observed in the other
halide adducts, at 3650 and 1600 cm-1, while the band at 1660 cm-1 is attributed to the H2O bending
vibrational mode. This value is blue-shifted respect liquid water, which is expected to show a band
at 1610 cm-1 [12]. For the water molecule, the vibration mode is reported at 1595 cm-1, while the
symmetric and asymmetric stretches appear at 3657 and 3756 cm-1, respectively. In the MIR
spectrum, the asymmetric stretching of water appears as a broad band at 3667 cm-1, overlapping
with the bridging OH stretching. At 3167 cm-1 we can observe the C4pz-H stretching, and the C=C
and C=N stretchings can be attributed to the peaks at 1542 and 1504 cm-1, respectively. C-F
stretching modes are observed as intense bands at 1254 and 1113 cm-1.
In the FIR spectrum of 2, the absorption of the Cu-O bond is shown at 489 cm-1 (slightly blue
shifted if compared to the Cl- or Br- adducts, 2a and 2b). The Cu-N bond absorption appears at 295
cm-1, again blue shifted when compared to the similar halide structures (291 cm-1 for the Cl- adduct,
2a and 287 cm-1 for the Br- adduct 2b). The very weak band at 522 cm-1, present only in the water
encapsulated adduct 2, might be attributed to the νL (hindered rotation, at 600 cm-1 for hydrogen
networked water).
The NIR spectra of compounds 2 (Figure 1) and 2a-d shows weak bands due to the O-H
combination bands of the fundamental vibration modes of water and hydroxyl groups. The bands at
1398 (first vibrational overtone), 1614, 2187 and 2404 nm are attributable to overtones of OH and
water, present in all the previously investigated adducts. In compound 2, on the contrary to those
observed for other adducts, the presence of additional bands, likely due to hydrogen bonding
networks, such as 2153 and 2353 nm were observed. These bands were reported in the NIR spectra
of ice [13]. Around 1896 nm, a medium sharp band is present, likely due to a combination of O-H
stretch and H-O-H bending modes (1900 nm for liquid water). A broad large band going from 1870
to 2050 nm might be due to physically adsorbed water [14].

Figure 1. NIR spectrum of compound 2 in the region 1000-2500 nm.
X-ray crystal structure analyses. The dinuclear nature of the compound [Cu-(3,5-
(NO2)2pz)(PPh3)]2, 1, (pz = 3,5-bis(dinitro)-1H-pyrazolate anion), has been evidenced by single
crystal X-ray diffraction analysis. The ORTEP view of the molecule is reported in Figure 2,
together with the atom labelling scheme. The most important bond distances and angles are reported
in the caption. Each copper atom is trigonally coordinated considering the two nitrogen atoms of the
bridging ligands and the phosphorous atom of the phosphane molecule. The coordination around the
copper atoms deviates significantly from the planarity, atoms Cu1 and Cu2 being out of the
pertinent coordination plane by 0.1924(4) and 0.2674(4) Å respectively. The six-member Cu-[N-
N]2-Cu ring presents a boat conformation, but considering that the copper atoms lie out of the
pyrazolate average planes, with deviations spanning from a minimum of 0.0231(4) Å for Cu1 with
respect to the N5N6C4C5C6 ring up to 0.3376(4) Å for Cu2 with respect to the N1N2C1C2C3 ring,
the resulting boat conformation is slightly twisted. The crystal packing of the compound is built up
by a strong network of Van der Waals interactions between the nitro groups and between the nitro
groups and the nitrogen atoms of the pyrazolate ring of adjacent molecules.

Figure 2. Ortep view of [Cu-(3,5-(NO2)2pz)(PPh3)]2, 1. The phosphane ligands have been drawn sa
a wireframe model. Ellipsoids, when shown, are at the 30% level. Selected bond distances (Å) and
angles (°): N1-Cu1 2.0217(19), N5-Cu1 1.998(2), P1-Cu1 2.1981(7), N2-Cu2 1.974(2), N6-Cu2
2.004(2), P2-Cu2 2.1812(8); N5-Cu1-N1 104.09(8), N5-Cu1-P1 126.42(6), N1-Cu1-P1 126.87(6),
N2-Cu2-N6 102.17(8), N2-Cu2-P2 132.41(6), N6-Cu2-P2 120.20(6).
The asymmetric unit of compound 2 is depicted in Figure 3. It contains one sixth of the neutral
copper(II) hexanuclear metal core [Cu(µ-OH)(η2,µ-(CF3)2pz’)]6 [pz’ = 3,5-bis(trifluoromethyl)-1H-
pyrazolate anion], an inversion centre is sited in the middle of the core and a 3-fold axis passes
through that location. Selected bond distances and angles are given in the legend of Figure 3. The
copper atoms present distorted square-planar geometries, as expressed by the Houser (τ4) 39
parameter of 0.29, join five-membered Cu2N2O rings and ultimately give rise to a large Cu6(N2O)6
crown-type assembly. The structure can also be envisaged as a circular zig-zag Cu6O6 cluster,
where the metal cations stand in the least-square plane defined by those atoms; the bridging η2-
pyrazolate moieties are alternatively positioned above and below this plane, the minimum
intramolecular Cu···Cu distance is 3.1425(17) Å and the Cu–O and Cu–N bond lengths are 1.917(2)
and 1.970(3) (average values) Å, respectively. The structure is stabilized by intermolecular
hydrogen bond interactions (Figure 3) involving the pyrazolate CH groups (as donors) and the F1
atoms (as acceptors) of vicinal complexes.

Figure 3. The asymmetric unit with the atom labelling scheme (left) and the structure (right) of
compound 2, also showing the donor (carbon)···acceptor (fluorine) contact interactions (in dashed
light blue lines). Symmetry operations to generate equivalent atoms: i) 1.67-x+y,1.3(3)-x,1/3+z; ii)
1.3(3)-y,-1/3+x-y,-1/3+z. Selected bond distances (Å) and angles (º): N1‒Cu1 1.972(3), N2‒Cu1
1.965(3), O1‒Cu1 1.918(2), N1‒N2 1.346(4), C1‒N1 1.340(4), C3‒N2 1.342(4), C4‒F3 1.328(4),
C5‒F5 1.340(4); O1‒Cu1‒N2 86.04(11), O1‒Cu1‒N1 97.84(11), N2‒ Cu1‒N1 163.86(11),
O1‒Cu1‒O1 155.30(14). Hydrogen bond interaction C2‒H2···F1i: D···A 3.279(7) Å, D‒H···A
153º.
Catalytic studies. Compounds 1 and 2 act as very effective homogeneous catalysts towards the neat
microwave (MW) assisted peroxidative (with aq. tert-butyl hydroperoxide, TBHP) oxidation of
cyclohexane to cyclohexanol, cyclohexanone and cyclohexyl hydroperoxide (Scheme 3).

Scheme 3 – Microwave-assisted neat oxidation of cyclohexane to cyclohexyl hydroperoxide,
cyclohexanol and cyclohexanone with tert-butyl hydroperoxide catalysed by the Cu complexes 1 or
2.
The formation of the hydroperoxide was proved by Shul’pin’s method [15] and allowed us to
estimate the real concentrations of alkyl hydroperoxide, alcohol and ketone: the addition of PPh3
prior to the GC analysis of the products resulted in a marked increase of the amount of
cyclohexanol (due to the reduction of CyOOH by PPh3, with the formation of phosphane oxide) and
a corresponding decrease in the amount of cyclohexanone. The formation of cyclohexyl
hydroperoxide (a typical intermediate product in radical-type reactions), along with the complete
suppression of the catalytic activity upon the introduction of a radical trap (Ph2NH, Figure 4) to the
reaction mixture, supports the hypothesis of a free-radical mechanism for the cyclohexane oxidation
carried out in this study. The radicals tert-BuOO• and tert-BuO•[16] could be produced in the
catalyst promoted decomposition of TBHP with the formation of a reduced form of the catalyst and
an hydroxo-Cu species (precursor of a tert-butylperoxide copper species). Those radicals could then
react with cyclohexane (CyH) giving rise to the cyclohexyl radical Cy• upon hydrogen abstraction.
Cy• reacts with oxygen, leading to CyOO•. CyOOH can be formed, e.g., upon hydrogen abstraction
from tert-BuOOH by CyOO•. Metal-assisted decomposition of CyOOH to CyO• would then lead to
CyOH and CyO products.
A very high yield, up to 58% (2) or 51% (1) of oxygenated products, is obtained under optimized
conditions: 0.5 h (2) or 1.5 h (1) of MW irradiation at 100 ºC (see Figure 5 and Table S1, Electronic
Supporting Information), using a 0.2 % molar ratio of the copper catalyst relative to the substrate, in
the presence of the 2,2,6,6-tetramethyl-piperidinyloxyl radical (TEMPO, 2.5 % molar ratio vs.
substrate).

60.0
50.0
40.0
30.0
20.0
10.0
0.0
none
TEMPO
Hpca
Ph2NH
Figure 4 - Effect of different additives on the yield of cyclohexanol and cyclohexanone obtained by
microwave-assisted neat oxidation of cyclohexane with THBP, catalysed by 2 (0.1% molar vs.
substrate).
Complexes 1 and 2 were shown to be much more active than Cu(I) or Cu(II) salts (Table S1),
suggesting the favourable involvement of the ligands in the metal-assisted steps of this catalytic
oxidation reaction.

Figure 5 - Effect of the reaction time, catalyst 2 amount and TEMPO additive on the yield of
cyclohexanol and cyclohexanone obtained by microwave-assisted neat oxidation of cyclohexane
with THBP.
For the Cu(II) catalytic system, the amount of catalyst plays a significant role, as depicted in
Figures 6 and 7. The increase from 1 to 5 µmol of 2 in the reaction medium leads to a yield
increment from 22 to 37%, whereas 10 µmol of 2 allows the maximum yield to be reached faster (in
1 hour, instead of the 2 hours of MW irradiation needed for 5 µmol of 2). The effect of the quantity
of the catalyst on the yield of products is not so evident for the Cu(I) system, compound 1.
Moreover, addition of small amounts (2.5 mol% vs. substrate) of TEMPO to the reaction mixture
allows the maximum yield of cyclohexanol and cyclohexanone to be achieved after a very short
MW irradiation time of 0.5 or 1 h, for 10 or 5 µmol of 2, respectively (Figure 6). The same
behaviour is observed for the Cu(I) catalytic system, compound 1. The promoting effect of TEMPO
may be rationalized as follows: under the used oxidizing conditions TEMPO conceivably could be
oxidized to the oxoammonium species [17] and thus also operate as an oxidant to transform
cyclohexane into the corresponding oxygenated product, as well as acting as a hydrogen-atom
abstractor from TBHP, reinforcing the formation of tert-BuOO•. However, when added in higher
amounts, TEMPO can exhibit its well known inhibiting effect [10,18]: for 1, addition of 2.5, 5, 50
and 100 mol % vs. cyclohexane led to total (cyclohexanol and cyclohexanone) yields of 21.6, 21.4,
3.8 and 0.0 %, respectively. The alcohol to ketone ratio (A/K) is known as an indicator for catalyst
selectivity, reflecting the combined conversion of cyclohexane either directly to cyclohexanol or to
cyclohexyl hydroperoxide, which subsequently is reduced to the alcohol as a result of reduction
with triphenylphosphine [15]. In the present study, cyclohexanol is obtained in a larger amount than
cyclohexanone, the alcohol/ketone molar ratio is ca. 3 for 1 in additive-free media (Table S1). As
expected, the presence of TEMPO (a well-known promotor of alcohol oxidation) [19] promotes the
formation of ketone (the molar ratio decreases to ca. 1.7). For 2, the effect is only detectable for the
highest catalyst amount used (0.2 % vs. substrate).

50
45
40
35
30
25
20
15
10
5
0
0
0.5
1
1.5
2
2.5
3
Reaction time / h
1 micromol
5 micromol
10 micromol
5 micromol
10 micromol
Figure 6 - Effect of the reaction time and catalyst (— 2 or ---- 1) amount on the yield of
cyclohexanol and cyclohexanone obtained by additive-free microwave-assisted neat oxidation of
cyclohexane with THBP.
The catalytic activity of 1 and 2 is also sensitive to temperature, as depicted in Figure 7 for the
catalyst 2.
50
40
30
MW 60 ºC
20
10
0
MW 100 ºC
r. t.
0
0.5
1
1.5
2
2.5
3
Reaction time / h

Figure 7. Effect of reaction temperature on the yield of cyclohexanol and cyclohexanone obtained
by the additive-free neat oxidation of cyclohexane with THBP, catalysed by 2 (0.1% molar vs.
substrate).
The promoting role of certain acids, in particular pyrazine carboxylic acid (Hpca), on the catalytic
oxidation of various cycloalkanes catalysed by metal complexes is well known [20]. In our catalytic
systems, the presence of Hpca has a strong inhibiting effect on the catalytic activity of both 1 and 2
(Figure 4). A similar behaviour was previously found [21].
Conclusions
A new route for the synthesis of [Bu4N][Cu6(3,5-pzCF3)6(OH)6 ⊃ X] ( X = Cl, Br, I and NO2) was
found, starting from neutral 3,5-pzH(CF3)2 and Cu2O as the source both of the metal and the base
(oxide) in aerated and wet acetonitrile. The reactions show lower yields when compared to that
previously reported [3c,4c], but it was proven that anions do not template these reactions and a
water encapsulated metallacycle, [Cu6(3,5-pzCF3)6(OH)6 ⊃ H2O], 2, was synthesized. In complex 2
the presence of the water molecules inside the cavity was analyzed by NIR spectroscopy and by
determining the rate constant of the water fast exchange reaction in acetone solution. Moreover, by
considering that the internal diameter of the cavity is 6.2 Å and the height of the channel is 7.6 Å on
average; these sizes can be compared to those of γ cyclodextrins formed by seven glucose
molecules connected by γ-1,4 glycosidic bonds. In the hexanuclear copper(II) host, the upper and
lower rim CF3 groups merge, making the entrance very polar, while in the cavity, the OH groups are
in a symmetric trans configuration, forming hydrophilic environments above and below the rim
with pseudo spherical hydrogen bonding symmetry; this environment makes the host able to
encapsulate spherical ions, but at the same time the circular disposition of electrophilic Cu(II) ions
makes the host able to recognize neutral polar nucleophilic molecules with the appropriate size. The
formation of tri or hexanuclear complexes is not a result that is easily repeated for similar pyrazoles:
when 3,5-dinitropyrazole is used neither the trinuclear Cu(I) nor the hexanuclear Cu(II) complexes
were obtained and the only product was that containing pyrazole, Cu(I) ions and the additional co-
ligand PPh3. The two complexes, [Cu2(µ-N,N-3,5-(NO2)2pz)2(PPh3)2], 1, and [Cu6(3,5-
pzCF3)6(OH)6 ⊃ H2O], 2, despite their structural differences, were successfully tested as catalysts
for the microwave-assisted neat oxidation of cyclohexane to a cyclohexanol and cyclohexanone
mixture, likely through a radical mechanism, affording considerably high yields (up to 58%) in
rather short reaction times (30 min for 2). The presented catalytic procedure leads to significantly
higher yields of cyclohexanol and cyclohexanone than those reported (although for considerably
different conditions) for copper complexes with related ligands, such as the C-scorpionate Cu(II)

complex [CuCl2(TpmOH)2] (TpmOH = 2,2,2-tris(pyrazol-1-yl)ethanol), 7% [22], copper
coordination polymers with pyrazolato-based tectons, 11% [21a] or based on trinuclear triangular
[Cu3(µ3-OH)(µ-pz)3]2+ units, 36% [23]. Moreover, our catalytic protocol (TBHP/MW) is very fast,
solvent-free and uses a green energy source.
Experimental Section
Elemental analyses (C, H, N, S) were performed in-house with a Fisons Instruments 1108 CHNS-O
Elemental Analyser. Melting points were taken on an SMP3 Stuart Scientific Instrument. MIR
spectra were recorded from 4000 to 600 cm-1 with a Perkin-Elmer SPECTRUM ONE System FT-
FIR instrument. NIR spectra were recorded from 4000 to 600 cm-1 with a Perkin-Elmer
SPECTRUM ONE System FT-IR instrument. IR annotations used: br = broad, m = medium, s =
1
31
strong, sh = shoulder, vs = very strong, w = weak and vw = very weak. H and P NMR spectra
1
31
were recorded on an Oxford-400 Varian spectrometer (400.4 MHz for H and 162.1 MHz for P).
1
Chemical shifts, in ppm, for H NMR spectra are relative to internal Me4Si. 31P NMR chemical
shifts were referenced to an 85% H3PO4 standard. The 31P NMR spectroscopic data were
1
accumulated with H decoupling. NMR annotations used: br = broad, d = doublet, dd = double
doublet, t = triplet, m = multiplet, s = singlet. Electrospray mass spectra (ESI-MS) were obtained in
the positive- or negative-ion mode on a Series 1100 MSD detector HP spectrometer, using an
acetonitrile or methanol mobile phase. The compounds were added to reagent grade acetonitrile to
give solutions of an approximate concentration of 0.1 mM. These solutions were injected (1 µL)
into the spectrometer via an HPLC HP 1090 Series II fitted with an auto-sampler. The pump
delivered the solutions to the mass spectrometer source at a flow rate of 300 µl min-1, and nitrogen
was employed both as a drying and nebulising gas. Capillary voltages were typically 4000 and 3500
V for the positive- and negative-ion modes, respectively. Confirmation of all major species in this
ESI-MS study was aided by comparison of the observed and predicted isotope distribution patterns,
the latter calculated using the IsoPro 3.1 computer program. The used solvents were HPLC grade
and they were used as purchased, unless the reactions were water and oxygen sensitive, in which
case, anhydrous and radical free THF was obtained by treating the solvent with Na/acetophenone
under a N2 atmosphere. 3,5-Bis(trifluoromethyl)-1H-pyrazole and other chemicals were purchased
by Sigma Aldrich and used without further purification. The 3,5- dinitropyrazole [24] and the
complex [Cu(3,5-(CF3)2pz)]3 were prepared as previously described [3c,25].
Synthesis of [Cu2(µ-N,N-3,5-(NO2)2pz)2(PPh3)2], 1.

To a mixture of Ph3P (0.174 g, 0.66 mmol) and Cu(BF4)2 (0.104 g, 0.44 mmol) in dry THF, the
sodium pyrazole salt (0.08 g, 0.44 mmol) was added and the suspension was stirred overnight at
room temperature. The orange suspension was evaporated under vacuum to give an orange solid.
The solid was dissolved in dichloromethane and extracted 3 times with 10 ml water. The organic
phase was dried with Na2SO4, filtered over a paper filter and concentrated. The solution was layered
with hexane and orange crystals of 1 were recovered.
Characterization of 1: Yield 78 %. M.p: 121-123 °C. IR (cm-1): 3154 (w), 3051.5 (w), 1586 (w),
1539.7 (s), 1492 (s), 1479 (s,sh), 1455 (m), 1436 (m), 1368 (s), 1329 (s), 1296 (m), 1222 (w), 1182
(s), 1161 (m), 1097 (s), 1076 (m), 1047 (m), 1025 (m), 1010 (w), 997 (w), 967 (m), 925 (w), 915
1
(w), 833 (s), 812 (s), 741 (s), 706 (vs), 691.05 (vs). H NMR (acetone-d6, δ, ppm): 7.58 (s, 1H),
31
7.39 (m, 3H), 7.32 (m, 12H). P NMR (acetone-d6, δ, ppm): 3.76 (s). ESI (-) MS (CH3CN; m/z) :
377 (100) [(3,5(NO2)2pz)2 + Cu]-, 157 (63) [3,5(NO2)2pz]-. ESI (+) MS (CH3CN; m/z): 603 (m/z),
587 (100) [PPh3)2 + Cu]+; 366 (61). Elemental analysis for C42H42Cu2N8O8P2 Calc.: C, 52.33; H,
3.34; N, 11.60; Found: C, 52.29; H , 3.38; N, 11.58 %.
Synthesis of [{trans-Cu6(µ-OH)6(µ-3,5-(CF3)2pz}6 H2O], 2.
Method A: {[3,5-(CF3)2Pz]Cu}3 (0.040 g, 0.050 mmol) was dissolved in 5 ml of MeCN (HPLC
grade). The reaction mixture was stirred for 10 min and then left in air. Slowly the solution became
blue and after few days blue crystals of compound 2 were formed.
Method B: Solid 3,5 trifluoromethyl pyrazole (0.100 g, 0.49 mmol) was dissolved in 5 ml of MeCN
(HPLC grade) in air; to this solution solid Cu2O (0.035 g, 0.245 mmol) was added. The resulting
reaction mixture was left stirring for three days at 60 °C. After filtering on a celite bed, the solution
was left to evaporate at room temperature. A blue microcrystalline solid was collected after a few
days from a dark green solution.
Characterization of compound 2. Yields: Method A 82%, Method B 45%. M.p. 242 °C with
decomposition. IR (cm-1): 3660, 3563, 3168, 1660, 1561, 1541, 1503, 1336, 1254, 1150, 1113,
1
1023, 935, 829, 758, 734, 729. H NMR (acetone-d6, r. t., δ, ppm): 25.97 (s, pzC4-H). ESI(-) MS
(CH3CN, m/z): 203.1 m/z (100) [CF3)2pz], 469.1 (18), 648.7 (20), 1737.2 (100)
[Cu6((CF3)2pz)6(OH)6Cl)]. ESI (+) MS (CH3CN, m/z): 242.4 m/z (100) [Bu4N]. Elemental analysis
for C30H14Cu6F36N12O7 + 2CH3CN: Calc.: C, 22.86; H, 1.12; N, 10.88; Found: C, 23.04; H, 1.12; N,
10.49%.
Synthesis of 2a-d by method B.

3,5-Trifluoromethyl-1H-pyrazole (0.050 g, 0.245 mmol) and Cu2O were dissolved in 10 ml of
MeCN. Then [Bu4N]Cl (2a, 0.011 g, 0.040 mmol), [Bu4N]Br (2b, 0.013 g, 0.040 mmol), [Bu4N]I
(2c, 0.0147 g, 0.040 mmol) or [PPNNO2] (2d, 0.014, 0.0375 mmol) was added to the solution.The
reaction mixture was left to stir for 2 h. The precipitate formed was filtered on Celite, washed with
acetone and finally dried under an air flow. Slowly the solution became blue or green, was dried
under an air flow and the solid 2a (Cl), 2b (Br), 2c (I) or 2d (NO2) product was isolated as a
microcrystalline powder by slow evaporation. The yields are of 2a (40%;), 2b (35%;), 2c (37%;),
2d (30%). The spectroscopic and analytical characterizations were compared to those already
reported [3c,4c].
X-ray crystal structure determination
Crystal data for 1 and 2 were collected at 203 (1) or 150 K (2) on a Bruker APEX II single-crystal
diffractometer, working with Mo-Kα graphite monochromatic radiation (λ = 0.71073 Å) and
equipped with an area detector. The raw frame data [20 (1) or 0.5 (2) s per frame scan time] for a
sphere of diffraction data were processed using the SAINT software [26], with a correction for
absorption being made using SADABS [27]. The structures were solved by direct methods with
SHELXS-97 (1) or SIR97 (2) [28] and refined against F2 with SHELXL-2014/7 [27] using
anisotropic thermal parameters. The hydrogen atoms attached to carbon atoms were inserted in
calculated positions, their Uiso (H) were defined as 1.2Ueq of the parent carbon atoms. The
pyrazolyl hydrogen atom in 2 was inserted in a calculated position and refined using a riding model.
The hydroxyl hydrogen atom in 2 was located in the difference Fourier synthesis and refined with
the help of distance restraint. During the refinement of this structure (2), electron density peaks
were located and believed to be of highly disordered water molecules. All the attempts made to
model the solvent molecules were not successful and they were removed using the SQUEEZE
routine from Platon [29]. This procedure was applied to recover 123 electrons per unit cell (total
volume 602 Å3). Lattice solvent water molecules are thus present as ca. 12 water molecules per unit
cell. These water molecules were not included in the cif. Details for the X-ray data collection are
reported in Table 1.
Table 1. Details for the X-ray data collection for 1 and 2
Complex
1
2
Formula
C42H32Cu2N8O8P2
965.77
C30H12Cu6F36N12O6
1701.76
Molecular weight
Crystal system
Triclinic
Trigonal

Space group
P-1
R-3
a/Å
10.093(2)
12.325(2)
19.251(3)
72.496(3)
87.743(3)
66.218(3)
2080.9(6)
2
21.863(5)
b/Å
21.863(5)
c/Å
10.076(5)
α/°
90
β/°
90
γ/°
120
Volume, Å3
4171(3)
Z
3
Dcalc/g cm-3
F(000)
1.541
2.032
984
2466
µ(Mo-Kα)/mm-1
Reflections collected
Unique reflections
Observed reflections [I>2σ(I)]
R, wR [I > 2σ(I)]
R, wR [all data]
CCDC ref code
1.163
2.425
28774
20374
10015
1707
7113 [Rint = 0.0486]
R = 0.0400; wR = 0.0860
R = 0.0673; wR = 0.0969
1478672
1282 [Rint = 0.0793]
R = 0.0319; wR = 0.0635
R = 0.0601; wR = 0.0692
1495587
2
2 2
R = Σ||Fo| – |Fc||/Σ|Fo|. b wR2 = [Σ[w(Fo – Fc2)2]/ Σ[w(Fo ) ]]1/2
Catalytic studies. The catalytic tests under microwave irradiation (MW) were performed in a
focused Anton Paar Monowave 300 microwave reactor using a 5 mL capacity reaction tube with a
10 mm internal diameter, fitted with a rotational system and an IR temperature detector. Gas
chromatographic (GC) measurements were carried out using a FISONS Instruments GC 8000 series
gas chromatograph with a FID detector and a capillary column (DB-WAX, column length: 30 m;
internal diameter: 0.32 mm) and the Jasco-Borwin v.1.50 software. The temperature of injection
was 240 ºC. The initial temperature was maintained at 100 ºC for 1 min, then raised at 10 ºC/min to
180 ºC and held at this temperature for 1 min. Helium was used as the carrier gas. GC-MS analyses
were performed using a Perkin Elmer Clarus 600 C instrument (He as the carrier gas). The
ionization voltage was 70 eV. The gas chromatography was conducted in the temperature-
programming mode, using a SGE BPX5 column (30 m × 0.25 mm × 0.25 µm). Reaction products

were identified by comparison of their retention times with known reference compounds and by
comparing their mass spectra to fragmentation patterns obtained from the NIST spectral library
stored in the computer software of the mass spectrometer.
Appendix A. Supplementary data
CCDC reference codes 1478672 and 1495587 contain the supplementary crystallographic data for
compounds 1 and 2, respectively. These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
Acknowledgements
R.G. is gratefull to FAR (Fondi di Ateneo dell’Università degli studi di Camerino) and CIRCSMB
(Consorzio Interuniversistario per la Chimica dei Metalli con le Sostanze Biologiche). The financial
support from the Fundação para a Ciência e a Tecnologia (FCT), Portugal for the fellowship
SFRH/BD/52371/2013 to N.M.R. Martins and the UID/QUI/00100/2013, PTDC/QEQ-
ERQ/1648/2014 and PTDC/QEQ-QIN/3967/2014 projects is gratefully acknowledged.
References
[1]
a) Chen, Z.; Meyer, T. J. Angew. Chem. Int. Ed. 52 (2013) 700-703.; b) Hoover, J. M.,
Ryland, B. L., Shannon S. S. J. Am. Chem. Soc. 135 (2013) 2357-2367.;c) Qi, Y.; Luan, Y.; Yu, J.;
Peng, X.; Wang, G. Eur. J. Inorg. Chem 21 (2015) 1589-1597; d) Kirillov, A. M.; Kopylovich, M.
N.; Kirillova, M.; Haukka, M.; Guedes Da Silva, M. F. C.; Pombeiro, A. J. L. Angew. Chem. Int Ed
44 (2005) 4345-4349; e) Santagostini, L.; Gullotti, M.; Pagliarin, R.; Monzani, E.; Casella, L.
Chem. Comm. (2003) 2186-2187; f) Shi, F.-N.; Silva, A. R.; Rocha, J. J. Solid State Chem. 184
(2011) 2196–2203; g) Casiello, M., Monopoli, A., Cotugno, P., Milella, A., Dell’Anna, M. M.,
Ciminale, F., Nacci, A. J. Mol. Catal. A: Chem. 381 (2014) 99–106; h) Mizuno, T. Nakai, T.,
Mihara, M., Heteroatom. Chem. 21 (2010) 99-102.
[2]
a) Kitajima, N., Moro-oka, Y. Chem. Rev. 94 (1994) 737-757; b) Klabunde, T.; Eicken, C.;
Sacchettini, J. C.; Krebs, B. Nature Struct. Biol. 5 (1998) 1084-1090.c) Piontek, K.; Antorini, M.;
Choinowski, T. J. Biol. Chem. 277 (2002) 37663-37669; d) Matoba, Y.; Kumagai, T.; Yamamoto,
A.; Yoshitsu, H.; Sugiyama, M. J. Biol. Chem. 281 (2006) 8981-8990.
[3]
a) Cañon-Mancisidor, W.; Gomez-Garcia, C. J. Guillermo, Vega, M. E. A.; Spodine, E.;
Venegas-Yazigi, D.; Coronado, E. Chem. Sci. 5 (2014) 324-332; b) Wu, T.; Yi, B.-H.; Li, D. Inorg

Chem. 44 (2005) 4130-4132; c) Mohamed, A. A.; Chiarella, G.; Melgarejo, D.; Burini, A. Galassi
R., Ricci, S.; Santini, C.; Fackler, J. P. Jr. Inorg. Chem. 50 (2011) 1014-1020.
[4]
a) Sheikh, Kimanshu, J. A.; Jena, S.; Adhikary, A.; Khatua, S.; Konar, S. Inorg Chem. 52
(2013) 9717-9719; b) Ferrer, S.; LLoret, F.; Bertomeu, I.; Alzuet, G., Borras, J.; Garcia-Granda, S.;
Liu-Gonzalez, M.; Haasnoot, J. G. Inorg Chem. 41 (2002) 5821-5830; c) Mohamed, A. A.; Burini,
A.; Galassi, R.; Paglialunga, D.; Galan-Mascaros, J-R.; Dunbar, K. R.; Fackler, J. P. Jr. Inorg.
Chem. 46 (2007) 2348-2349.
[5]
a) Prathap, K. J.; Maayan G. Chem Commun. 51 (2015) 11096-11099, b) Que, L. Jr.,
Tolman, W. B. Nature 455 (2008) 333-340.
[6]
a) Lupidi, G.; Marchetti, F.; Masciocchi, N.; Reger, D. L.; Tabassum, S.; Astolfi, P.;
Damiani, E.; Pettinari, C. J. Inorg. Biochem. 104 (2010) 820–830; b) Mutti, F. G.; Zoppellaro, G.;
Gullotti, M.; Santagostini, L., Pagliarin, R., Andersson, K. K.; Casella, L. Eur. J. Inorg. Chem.
(2009) 554-566.
[7]
a) Hubin, T. J. Coord. Chem. Rev. 241 (2003) 27-46; b) Dhal, P. K., Arnold, F. H.
Macromolecules 25 (1992) 7051-7059.
[8]
[9]
Galassi, R.; Burini, A.; Mohamed, A. Eur. J. Inorg. Chem. (2012) 3257-3261.
Ullmann’s Encyclopedia of Industrial Chemistry, 6th ed., Wiley-VCH, Weinheim, (2002).
b) Weissermel, K.; Arpe, H.J. Industrial Organic Chemistry, 2nd ed., VCH Press, Weinheim,
(1993). c) Clark, J.H.; Macquarrie, D.J. Handbook of Green Chemistry and Technology, Wiley,
New Jersey, (2002).
[10] a) Advances in Organometallic Chemistry and Catalysis, The Silver/Gold Jubilee ICOMC
Celebratory Book, Vol (A. J. L. Pombeiro Ed.), J. Wiley & Sons, (2014). ISBN: 978-1-118-51014-
8. b) Strukul, G.; Scarso, A. Environmentally Benign Oxidants. In Liquid Phase Oxidation via
Heterogeneous Catalysis, Organic Synthesis and Industrial Applications; vol. (Eds. Clerici, M.G.,
Kholdeeva, O.), John Wiley & Sons, New Jersey, (2013).
[11] Woods, M.; Aime, S.; Botta, M.; Howard, J. A. K.; Moloney, J. M.; Navet, M.; Parker, D.;
Port, M.; Rousseaux, O. J. Am. Chem. Soc. 122 (2000) 9781-9792.
[12] Primer, M.; Pichat, P.; Mathieu, M. V. J. Phys. Chem. 75 (1971) 1216-1220.
[13] Taffin, C.; Grasset, O.; Le Menn, E.; Bollengier, O.; Giraud, M.; Le Mouélic, S. Science 61
(2012) 124-134.

[14] Takeuchi, M.; Martra, G.; Coluccia, S.; Anpo, M. J. Phys. Chem. B 109 (2005) 7387-7391.
[15] a) Shul’pin, G. B. Transition Metals for Organic Synthesis, vol. 2 (M. Beller and C. Bolm
Eds.), 2nd edition, Wiley-VCH, New York, (2004). b) Shul’pin, G.B.; Nizova, G.V. React. Kinet.
Catal. Lett. (1992), 48, 333–338; c) Shul’pin, G.B.; Matthes, M. G.; Romakh, V. B.; Barbosa, M. I.
F.; Aoyagi, J. L.; Mandelli, T. D. Tetrahedron 64 (2008) 2143-2152, d) Shul’pin, G.B. Dalton
Trans. 42 (2013) 12794-12818; e) Shul’pin, G.B. Org. Biomol. Chem. 8 (2010) 4217-4228; f)
Shul’pin, G. B. Mini-Rev. Org. Chem. 6 (2009), 95-104.
[16] a) Allen, E.; Walvoord, R.R.; Padilla-Salinas, R.; Kozlowski, M.C. Chem. Rev. 113 (2013)
6234-6458. b) Lin, L.; Juanjuan, M.; Liuyan, J.; Yunyang, W. J. Mol. Catal. A Chem. 291 (2008) 1-
4. c) Venâncio, A.I.F.; Kuznetsov, M.L.; Guedes da Silva, M.F.C.; Martins, L.M.D.R.S.; Fraústo da
Silva, J.J.R.; Pombeiro, A.J.L. Inorg. Chem., 41 (2002) 6456-6467. d) Dragancea, D.; Talmaci, N.;
Shova, S.; Novitchi, G.; Darvasiova, D.; Rapta, P.; Breza, M.; Galanski, M.; Kozisek, J.; Martins,
N. M. R.; Martins, L. M. D. R. S.; Pombeiro, A. J. L.; Arion, V. B. Inorg. Chem. 55 (2016) 9187-
9203.
[17] a) Bobbit, J. M.; Brückner, C.; Merbouh, N. Org. React. 74 (2009) 103-424. b) Angelin, M.;
Hermansson, M.; Dong, H.; Ramström, O. Eur. J. Org. Chem. 19 (2006) 4323-4326.
[18] Slaughter, L. M.; Collman, J.P.; Eberspacher, T.A.; Brauman, J. Inorg. Chem. 43 (2004)
5198-5204.
[19] Kopylovich, M.N.; Ribeiro, A.P.C.; Alegria, E.C.B.A.; Martins, N.M.R.; Martins,
L.M.D.R.S.; Pombeiro, A.J.L. Adv. Organomet. Chem. 63 (2015) 91-174.
[20] a) Martins, L. M. D. R. S.; Pombeiro, A. J. L. Coord. Chem. Rev. 265 (2014) 74-88. b)
Milunovic, M. N. M.; Martins, L. M. D. R. S.; Alegria, E. C. B. A.; Pombeiro, A. J. L.; Krachler,
R.; Trettenhahn, G.; Turta, C.; Shova, S.; Arion, V. B. Dalton Trans. 42 (2013) 14388-14401. c)
Sutradhar, M.; Kirillova, M. V.; Guedes da Silva, M. F. C.; Martins, L. M. D. R. S.; Pombeiro, A. J.
L. Inorg. Chem. 51 (2012) 11229-11231. d) Silva, T. F. S.; Martins, L. M. D. R. S.; Guedes da
Silva, M. F.; Kuznetsov, M. L.; Fernandes, A. R.; Silva, A.; Santos, S.; Pan, C.-J.; Lee, J.-F.;
Hwang, B.-J.; Pombeiro, A. J. L. Chem. Asian J. 9 (2014) 1132-1143. e) Martins, L.M.D.R.S.;
Martins, A.; Alegria, E.C.B.A.; Carvalho, A.P.; Pombeiro, A. J. L Appl. Catal. A: 464 (2013) 43-
50; f) Martins, L.M.D.R.S.; Peixoto de Almeida, M.; Carabineiro, S.A.C.; Figueiredo, J. L.
Pombeiro, A. J. L. ChemCatChem 5 (2013) 3847-3856.
[21] a) Timokhin, I.; Pettinari, C.; Marchetti, F.; Pettinari, R.; Condello, F.; Galli, S.; Alegria, E.
C. B. A.; Martins, L.M.D.R.S.; Pombeiro, A. J. L. Cryst. Growth Des. 15 (2015) 2303-2317. b)

Martins, L.M.D.R.S.; Alegria, E.C.B.A.; Smoleński, P.; Kuznetsov, M.L.; Pombeiro, A.J.L. Inorg.
Chem. 52 (2013) 4534-4546. c) Fernandes, R. R.; Lasri, J.; Guedes da Silva, M. F. C.; da Silva, J.
A. L.; Fraústo da Silva, J. J. R.; Pombeiro, A. J. L. J. Mol. Catal. A: Chem. 351 (2011) 100-111. d)
Peixoto de Almeida, M.; Martins, L. M. D. R. S.; Carabineiro, S. A. C.; Lauterbach, T.; Rominger,
F.; Hashmi, A. S. K.; Pombeiro, A. J. L.; Figueiredo, J. L. Catal. Sci. Technol. 3 (2013) 3056-3069.
e) Martins, L.M.D.R.S.; Nasani, R.; Saha, M.; Mobin, S.M.; Mukhopadhyay, S.; Pombeiro, A.J.L.
Molecules 20 (2015) 19203-19220.
[22] Silva, T.F.S.; Silva, M.F.C.G.; Mishra, G.S.; Martins, L.M.D.R.S.; Pombeiro, A. J. L. J.
Organomet. Chem 696 (2011) 1310-1318.
[23] Contaldi, S.; Di Nicola, C.; Garau, F.; Karabach, Y.Y.; Martins, L.M.D.R.S.; Monari, M.;
Pandolfo, L.; Pettinari, C.; Pombeiro, A.J.L. Dalton Trans. (2009) 4928-4941.
[24] Galassi, R.; Ricci, S.; Burini, A.; Macchioni, A.; Rocchigiani, L.; Marmottini, F.; Tekarli, S.
M.; Nesterov, V. N.; Omary, M. A. Inorg. Chem. 52 (2013) 14124 -14137.
[25] Dias, H. V. R.; Polach, S. A.; Wang, Z. J. Fluorine Chem 103 (2000) 163-169.
[26] b) SMART Software User Guide, Version 5.1, Bruker Analytical X-ray Systems, Madison,
WI, 1999; c) SAINT Software User Guide, Version 6.0, Bruker Analytical X-ray Systems,
Madison, WI, 1999; G. M. Sheldrick, SADABS, Bruker Analytical X-ray Systems, Madison, WI,
1999; d) APEX II Software User Guide, SAINT, version 7.06a, SADABS, version 2.01, Bruker
AXS Inc., Madison, WI, 2008.
[27] Sheldrick, G. M. Acta Crystallogr., Sect. A: Found. Crystallogr. 64 (2008) 112-122.
[28] Altomare, A.; Burla, M. C., Camalli, M.; Cascarano, G. L.; Giacovazzo, C.; Guagliardi, A.;
Moliterni, A. G. G., Polidori, G., Spagna, R. J. Appl. Cryst. 32 (1999) 115-119.
[29] A.L. Spek, Single-crystal structure validation with the program PLATON J. Appl. Cryst. 36
(2003) 7-13

COPPER(I) AND COPPER(II) METALLACYCLES AS CATALYSTS FOR MICROWAVE ASSISTED SELECTIVE
OXIDATION OF CYCLOHEXANE
Rossana Galassi,* Oumarou Camille Simon, Alfredo Burini, Giorgio Tosi, Carla Conti, Claudia
Graiff, Nuno M. R. Martins, M. Fátima C. Guedes da Silva, Armando J. L. Pombeiro, Luísa M. D.
R. S. Martins*
Cu(I) and Cu(II) metallocycles were prepared with pyrazolates having CF3 or NO2 groups in the 3 and 5
positions. According to similar reaction routes, they yielded a hydrated hexanuclear metallocycle [(µ-
pz)Cu(µ-OH]6 and a dinuclear compound with an N2-Cu2(PPh3)2-N2 boat shaped core, respectively. Both
compounds are active as homogenous catalysts for MW assisted neat peroxidation of cycloalkanes by a
radical mechanism.