Novel bicyclic hexanuclear copper(I) aggregate: Structure and solid state 31P CPMAS NMR spectra of [(Cu3L3)2] and [Cu(PPh3)2L] complexes of N-(diisopropoxythiophosphinyl)-N′-phenylthiourea

Article abstract of DOI:10.1016/j.jorganchem.2008.10.010

A new complex of N-thiophosphorylthiourea PhNHC(S)NHP(S)(OiPr)₂ (HL) of formula [(Cu₃L₃)₂] has been synthesized and characterized by single crystal X-ray diffraction, FT-IR, ¹H, ³¹P NMR in

Full text of DOI:10.1016/j.jorganchem.2008.10.010

Journal of Organometallic Chemistry 694 (2009) 167–172
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Novel bicyclic hexanuclear copper(I) aggregate: Structure and solid state
31P CPMAS NMR spectra of [(Cu3L3)2] and [Cu(PPh3)2L] complexes
of N-(diisopropoxythiophosphinyl)-N0-phenylthiourea (HL)
Felix D. Sokolov a, Maria G. Babashkina a, Franck Fayon b,c, Aydar I. Rakhmatullin b,c, Damir A. Safin a,
,
*
Tania Pape d, F. Ekkehardt Hahn d
a A. M. Butlerov Chemistry Institute, Kazan State University, Kremlevskaya St. 18, 420008 Kazan, Russian Federation
b CEMHTI-CNRS, 1D Avenue de la Recherche Scientifique, 45071 Orléans Cedex2, France
c Université d’Orléans, Faculté des Sciences, Avenue du Parc Floral, BP 6749, 45067 Orléans Cedex2, France
d Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstrasse 36, D-48149 Münster, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 13 June 2008
Received in revised form 26 August 2008
Accepted 6 October 2008
Available online 14 October 2008
A new complex of N-thiophosphorylthiourea PhNHC(S)NHP(S)(OiPr)2 (HL) of formula [(Cu3L3)2] has been
synthesized and characterized by single crystal X-ray diffraction, FT-IR, 1H, 31P NMR in solution and by
31P CPMAS NMR spectroscopy in the solid state. A comparison of the structure and the spectral param-
eters of [(Cu3L3)2] with those of the mononuclear analogue [Cu(PPh3)2L] was performed. In the solid state
the aggregate [(Cu3L3)2] represents the first example of a spontaneous ‘‘side-by-side” association of two
neutral cyclic [Cu3L3] moieties using two Cu–S–Cu bridges formed by the sulfur atoms of the PS-groups.
The values of the 1J(31P–63,65Cu) and 2J(31P–31P) coupling constants of the [Cu(PPh3)2]+ moiety in the solid
state spectra are reported.
Keywords:
Copper(I) complexes
Crystal structures
MAS NMR spectroscopy
N-Thiophosphorylthiourea
Polynuclear complexes
Ó 2008 Elsevier B.V. All rights reserved.
1. Introduction
complexes like [Cu4{S2P(OR)2}4], [Cu6{S2P(OR)2}6] and [Cu8{S2-
P(OR)2}6(l
8-S)] (R = alkyl) [3,4].
Data available in the literature demonstrate, that complexes of
coinage metal cations with 1,3- and 1,5-bidentate ligands derived
from sulfur- or selenium-containing phosphines, exhibit a clear
propensity to form oligo- and polynuclear assemblies with struc-
tural features which depend on the conditions employed for their
preparation and the nature of the ligand [1–3]. The investigation
of the structure of such compounds, as a rule, is impossible without
the use of single crystal X-ray diffraction techniques. The situation
is further complicated by the problems encountered when
attempting to grow single crystals and the tendency for form olig-
omeric aggregates.
Therefore the development of spectroscopic methods has been
the focus of recent interest as such techniques not only provide
information on the structure of a given compound but can also
shed light on the mechanism of its formation. The literature con-
tains reports on the successful application of solid state nuclear
magnetic resonance for this purpose. For example, the solid-state
31P and 65Cu NMR spectroscopy allowed to determine successfully
selected structural parameters of some polynuclear copper(I)
This type of researches is important not only for the under-
standing of the fundamental laws of polynuclear coordination
structure formation, but also open the ways for further use of the
formed molecules. The complexes of phosphorus-, sulfur- or sele-
nium-containing ligands with coinage metals cations are of great
interest due to their photophysical properties [5,6], their applica-
tion for creation of chalcogenide nanoparticles [1c], and as models
for biological objects [7].
Contrary to the dithiophosphate ligands, there is a lack of infor-
mation about the structures of polynuclear copper(I) complexes
containing N-thiophosphorylated thioureas and thioamides,
RC(S)NHP(S)R02 (R = R02N, alkyl, aryl). The molecular structures of
three polynuclear CuI complexes namely the cyclic trimers
[Cu3{Et2NC(S)NP(S)(OPh)2}3] [8], [Cu3{MfC(S)NP(S)(OiPr)2}3] (Mf –
morpholyn-N-yl) [9] and of an ionic aggregate [Cu10{PhNHC(S)NP-
(S)(OEt)2}9]ClO4 [10], have been reported.
In this study, we describe the synthesis and the structural char-
acterization of the new N-thiophosphorylthiourea PhNHC(S)-
NHP(S)(OiPr)2 (HL) and of its polynuclear CuI aggregate [(Cu3L3)2]
(1) (Chart 1). To the best of our knowledge, compound 1 represents
the first example for the spontaneous ‘‘side-by-side” association of
the two neutral cyclic [Cu3L3] moieties to give a hexameric unit.
* Corresponding author. Fax: +7 843 254 37 34.
E-mail address: damir.safin@ksu.ru (D.A. Safin).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.10.010

168
F.D. Sokolov et al. / Journal of Organometallic Chemistry 694 (2009) 167–172
iPrO OiPr
P
OiPr
OiPr
N
S
NHPh
N
PhHN
N
P
S
Cu
iPrO
iPrO
PhHN
S
S
S
S
P
Cu
Cu
S
Cu
Cu
P
S
OiPr
OiPr
S
P
S
N
S
NHPh
Cu
S
iPrO
iPrO
N
NHPh
PhHN
N
P
iPrO OiPr
(1)
(2)
PhNH
N
OiPr
OiPr
P
S
S
Cu
Ph3P
PPh3
Chart 1. R = PhNH, R0 = OiPr.
Fig. 1. Comparison of a section of the IR spectra (Nujol) of HL (A), [Cu(PPh3)2L] (2)
(B), and [(Cu3L3)2] (1) obtained by reaction with CuI (C) and Cu(NO3)2 (D).
The structural and spectral parameters of the aggregate are dis-
cussed in comparison with the mononuclear analog [Cu(PPh3)2L]
(2), which has been reported earlier [11].
For complex
2 no such highfield shift has been observed
(D
dP = 0.2 ppm). This observation can be related to the smaller
electron-deficiency of the tetracoordinated copper(I) atom, coordi-
nated by two PPh3 donor groups in comparison with the coordin-
atively unsaturated tricoordinated copper atom in complex 1. An
increase in the Cu–S(P) bond order leads to an increase of the elec-
tron density at the phosphorus atom and causes its shielding. This
effect can be presented schematically, as an increase of the contri-
bution of the mesomeric structure [S@C–N@P–Sꢀ] during the neg-
ative charge delocalization in Lꢀ. The internuclear distances in the
molecular structure (see below) also testify to a greater degree of
participation of the sulfur atom of the P@S group in the formation
of the Cu–S(P) bonds in complex 1 in comparison with the similar
bonds in the mononuclear analogue 2.
The molecular structures of the hexameric 1 (Fig. 2) and mono-
nuclear complex 2 (Fig. 3) were determined by single crystal X-ray
diffraction (Table 1). Crystals of the complexes have been obtained
by slow crystallization from a dichloromethane/n-hexane solution,
1:2 (v/v).
2. Results and discussions
Reaction of the potassium salt KL with copper(I) iodide leads,
according to microanalytical data, to the formation of a complex
1 having the composition [CuL]. The reaction of KL with copper(II)
nitrate in ethanol leads to the same product. The identity of the
compounds received by these two methods, was confirmed by
spectroscopic methods (NMR, IR in the fingerprint area) and single
crystal X-ray diffraction.
The mononuclear complex [Cu(PPh3)2L] (2) has been obtained
by the reaction of KL with [Cu(PPh3)3I]. Complexes 1 and 2 were
purified by slow crystallization from a CH2Cl2/C6H14 solvent
mixture.
Electrospray ionization (ESI-MS) mass spectra of complex 1 did
not exhibit the [M+H]+ peak. The heaviest ion at m/z 1643 (20%)
corresponds to the cation [Cu5L4]+. The most intensive peaks in
the spectra correspond to the cation [Cu4L3]+ with m/z 1247. This
peak has also been observed for all mononuclear or polynuclear
CuI complexes of N-thiophosphorylthioureas [9,11]. Medium-
intensity (10–12%) peaks for [Cu3L2]+ cations were also observed
in the spectra of 1 and 2.
The IR spectra of the thiourea HL exhibit a medium strong band
for the P@S group stretching vibration centered at 638 cmꢀ1 [12].
The band is shifted to lower wavenumbers in the spectra of the
complexes 1 and 2 due to CuI coordination. A single absorption
peak has been observed in the spectra of the mononuclear complex
2, while three new bands at 561, 567, and 589 cmꢀ1 appear for the
polynuclear aggregate 1 (Fig. 1).
In the crystalline state complex 1 is a hexamer containing two
cyclic trimeric units [Cu3L3] connected by a pair of Cu(2)–S(5)–
Cu(2*) bridges. Symmetry transformations used to generate equiv-
alent atoms: ( ) 1 ꢀ x, ꢀy + 1, ꢀz + 1. The trimers are formed by the
*
bridging action of the
l
2-sulfur atoms of the CS-groups. The hexa-
mer is formed by the
l
2-sulfur atoms of the PS-groups of the
ligands.
The Cu(1) and Cu(3) atoms are found in a trigonal S3 environ-
ment. Atom Cu(2), participating in the bridging between trimers,
is coordinated in a distorted tetrahedral S3S0 environment. The val-
ues of the bond angles S(1)–Cu(2)–S(5) and S(2)–Cu(2)–S(5)* are
significantly distorted from the perfect tetrahedron value (Table 2).
The bridging distances Cu(2)–S(5)* is longer than the other Cu–S
bonds in the molecule (Table 2). The Cu–S bond distances in the cy-
cle Cu(2)–S(2)–C(14)–N(3)–P(2)–S(5) are noticeably increased
compared with the cycles at the Cu(1) and Cu(2) atoms.
The Cu(2)–Cu(2)* separation of 2.8016(9) Å measures close to
twice the van der Waals radius of Cu, 2.80 Å [14]. The other CuꢁꢁꢁCu
distances fall in the range 3.62–3.80 Å, showing no metal–metal
interactions.
The values of the bond distances in the six-membered cycles
Cu–S–C–N–P–S differ slightly. In comparison with the parent li-
gand HL [15] lengthening of the C@S and shortening of the C–N
bonds are observed upon complex formation. The same changes,
but to a lesser degree, has been observed for the P–N and P@S
bonds. The measured values for the internuclear distances are in
The broad and strong absorption peaks for the conjugated SCN
group at 1500–1530 cmꢀ1 (1) and 1530 cmꢀ1 (2) are characteristic
for the formation of S,S0-chelates [13]. The NH stretching vibrations
of NHP and NHPh groups in the thiourea HL are observed as two
peaks at 3100 and 3200 cmꢀ1. Unique bands related to the NHPh
groups in the 3320–3350 cmꢀ1 region were observed in the spec-
trum of the complexes 1 and 2.
The 31P NMR spectra of complexes 1 and 2 (CDCl3 solution) ex-
hibit a singlet for the phosphorus atom of the NPS group and one
set of signals of the protons of the ligand. No broadening of the sig-
nals and no indications for the presence of additional complexes
were found in the NMR spectra.
The signal for the phosphorus atom in the 31P NMR spectrum of
1 is highfield shifted by 4.7 ppm relative to the parent thiourea HL.

F.D. Sokolov et al. / Journal of Organometallic Chemistry 694 (2009) 167–172
169
Table 1
Crystal data, data collection and refinement details for 1 and 2.
1
2
Empirical formula
Formula mass
Crystal form
Space group
a (Å)
C78H120Cu6N12O12P6S12 C49H50CuN2O2P3S2
2369.64
Triclinic
P1
919.48
Triclinic
ꢀ
ꢀ
P1
13.1158(19)
14.102(2)
16.142(2)
105.228(3)
100.058(3)
107.719(3)
2636.7(7)
1
13.5916(19)
13.6610(19)
14.1437(19)
117.705(3)
92.922(3)
99.910(3)
2264.4(5)
2
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
Z
Dcalc (mg/m3)
Temperature (K)
F(000)
1.492
1.349
233(2)
153(2)
1224
960
l
[cmꢀ1
]
15.75
7.22
Number of recorded reflections
15204
10404
Number of independent reflections 9185 (Rint = 0.0378)
7842
(Rint = 0.0427)
Table 2
Selected bond lengths (Å), and bond angles (°) for 1.
Bond lengths
Cu(1)–S(3)
Cu(1)–S(4)
Cu(1)–S(1)
Cu(3)–S(2)
Cu(3)–S(6)
Cu(3)–S(3)
Cu(2)–S(1)
Cu(2)–S(2)
Cu(2)–S(5)
Cu(2)–S(5)*
S(1)–C(1)
2.2045(10)
2.2143(13)
2.2182(11)
2.1886(10)
2.2177(11)
2.2499(10)
2.2795(10)
2.3187(10)
2.3302(10)
2.4942(10)
1.757(4)
S(5)–P(2)
S(6)–P(3)
2.0035(14)
1.9896(13)
1.592(4)
1.602(3)
1.602(3)
1.293(5)
1.314(4)
1.303(4)
1.353(5)
1.415(5)
1.352(4)
1.417(4)
1.341(4)
1.420(4)
P(1)–N(1)
P(2)–N(3)
P(3)–N(5)
N(1)–C(1)
N(3)–C(14)
N(5)–C(27)
N(2)–C(1)
N(2)–C(2)
N(4)–C(14)
N(4)–C(15)
N(6)–C(27)
N(6)–C(28)
S(2)–C(14)
S(3)–C(27)
S(4)–P(1)
1.750(3)
1.763(4)
1.954(2)
Fig. 2. Crystal structure of complex [(Cu3L3)2] (1) (top) and the structure of the
polynuclear complex backbone (substituents are omitted for clarity).
Bond angles
S(1)–Cu(2)–S(2)
S(1)–Cu(2)–S(5)
S(2)–Cu(2)–S(5)
S(1)–Cu(2)–S(5)*
109.24(4)
126.16(4)
106.71(4)
105.74(4)
S(2)–Cu(2)–S(5)*
S(5)–Cu(2)–S(5)*
Cu(2)–S(5)–Cu(2)*
95.68(3)
109.09(3)
70.91(3)
square planes of the {Cu2S2} and {Cu3S3} cycles measures 70.93°.
Hydrogen bonds are not observed in the crystal structure of com-
plex 1.
In the molecular structure of complex [Cu(PPh3)2L] (2) (Fig. 3),
the copper(I) cation is in a P2S2 tetrahedral environment. The weak
distortion relative to a perfect tetrahedron (Table 3) reveal the ab-
sence of major steric hindrance.
The structures of the six-membered cycles of 1 and 2 have
many common features, typical for similar compounds [9,11], like
the flat N–C(S)–N–P–O fragment. The six-membered Cu(1)–S(2)–
C(1)–N(1)–P(1)–S(1) metallocycle in the mononuclear analogue
2, as well as in complex 1, are in a boat conformation. The P(1)
and S(2) atoms occupy apical positions.
The Cu(1)–S(2) bond is 0.04 Å longer than the Cu(1)–S(1) dis-
tance, which indicates the greater contribution of the S-enolic form
of Lꢀ. It is interesting to note, that the interatomic distances Cu(1)–
S(1) in the six-membered cycle of the complex 2 is significantly
larger than the distances Cu(1)–S(4), Cu(2)–S(5), Cu(3)–S(6) in
the complex 1. The lengthening of the Cu–S(P) bond in complex
2 is caused by the smaller acceptor ability of the coordinative-sat-
urated copper atom in a P2S2 environment in comparison with the
copper in a trigonal S3 or distorted-tetrahedral S3S0 environment.
Complex 2 forms centrosymmetric dimers due to formation of
intermolecular hydrogen bonds N(2)–H(2)ꢁꢁꢁS(2)*. Hydrogen bond
Fig. 3. Crystal structure of complex [Cu(PPh3)2L] (2).
a range which is characteristic for the complexes of N-thioacylam-
idophosphates and N-thiophosphorylated thioureas [13].
The four-membered metallocycle {Cu(2)–S(5)–Cu(2)*–S(5)*} is
flat. The six-membered metallocycle {Cu(1)–S(1)–Cu(2)–S(2)–
Cu(3)–S(3)} is in a twist-boat conformation with tops at the
Cu(1) and S(2) atoms. The dihedral angle between root-mean-

170
F.D. Sokolov et al. / Journal of Organometallic Chemistry 694 (2009) 167–172
Table 3
Selected bond lengths (Å), and bond angles (°) for 2.
Bond lengths
Cu(1)–P(2)
Cu(1)–P(3)
Cu(1)–S(2)
Cu(1)–S(1)
S(1)–P(1)
2.2623(7)
2.3181(7)
2.3303(7)
2.3730(7)
1.9716(9)
S(2)–C(1)
1.744(2)
1.6149(19)
1.312(3)
1.355(3)
1.412(3)
P(1)–N(1)
N(1)–C(1)
N(2)–C(1)
N(2)–C(2)
Bond angles
P(2)–Cu(1)–P(3)
P(2)–Cu(1)–S(2)
P(3)–Cu(1)–S(2)
P(2)–Cu(1)–S(1)
P(3)–Cu(1)–S(1)
115.00(3)
113.83(2)
107.22(3)
107.95(3)
106.41(2)
S(2)–Cu(1)–S(1)
P(1)–S(1)–Cu(1)
C(1)–S(2)–Cu(1)
N(1)–P(1)–S(1)
C(1)–N(1)–P(1)
105.80(2)
98.93(3)
101.24(8)
118.45(8)
126.92(16)
Fig. 4. The experimental (A) and simulated (B, C) of the solid state 31P{1H} CPMAS
NMR spectrum of the polynuclear complex [(Cu3L3)2] (1).
parameters are as follows: d(NH) 0.8400 Å, d(HS) 2.6700 Å, d(NS)
3.4704 Å, \(NHS) 161.0°. Symmetry transformations used to gen-
2
63Cu) and a homonuclear JPCuP coupling of about 121 Hz, which
was also measured using a two-dimensional spin echo MAS exper-
iment [17–19] (not shown), leads to a 16-lines multiplet for each of
the two inequivalent P sites. Each 16-lines multiplet consists of
two distinct quartets of doublets with relative intensities in the ra-
tio of about 2.3, in good agreement with the natural abundance of
the two copper isotopes (69.1% for 63Cu and 30.9% for 65Cu). An iso-
topic effect on the 1JCu–P scalar coupling is clearly observed and the
1J(63Cu–31P)/1J(65Cu–31P) ratio determined experimentally is of
about 0.938, as expected from the gyromagnetic ratios of the
63,65Cu isotopes. No isotopic effect on the 31P isotropic chemical
shift was observed experimentally. It should be noted that the 1JPCu
and 2JPCuP couplings were not observed in the solution NMR spectra
due to the fast exchange between free and bound triphenylphos-
phine groups. Table 4 gives the 31P NMR isotropic chemical shifts
and isotropic J-coupling constants determined from the simula-
tions of the CPMAS spectrum. The coupling constants obtained
are comparable to values found previously for complexes with
the same CuS2P2 complex core [9,20]. The P-site quantification ob-
tained from a single pulse spectrum is in agreement with the ex-
pected site multiplicities and the 63,65Cu isotopic abundances.
The simulation of the J-multiplet patterns (shown in Fig. 5) takes
in account ‘‘residual dipolar” effects due to the dipolar and aniso-
tropic scalar couplings between 31P and the quadrupolar copper
nuclei [21–23]. However, only the magnitude of this term was
fitted since both the 63,65Cu quadrupolar coupling constants and
J-coupling anisotropy are unknown. In order to get more detailed
interpretation of this spectrum, additional 63,65Cu NMR experi-
ments at very high magnetic field allowing to measure the
63,65Cu quadrupolar coupling parameters are in progress.
erate equivalent atoms: ( ) 1 ꢀ x, 1 ꢀ y, 1 ꢀ z.
*
To obtain information about the solid state structures of the CuI
complexes we have investigated polycrystalline samples of these
complexes using 31P MAS NMR spectroscopy (Table 4).
The crystal structure of 1 shows a centrosymmetric molecule,
containing three types of the phosphorus atoms (P1, P2, P3). This
observation is in good agreement with the CPMAS NMR data, con-
taining three singlets (Fig. 4). Simulation of the spectrum using the
DMFIT program [16] has enabled us to determine the exact values of
the chemical shifts of the phosphorus atoms and a ratio of the inte-
grated intensities 1/1/1 (Table 4).
A similar picture emerged previously in the spectrum of the tri-
meric associate [Cu3{MfC(S)NP(S)(OiPr)2}3] [9]. The 31P CPMAS
NMR data indicate the expected presence of three nonequivalent
P-sites in the solid state. This could be used for the identification
of the asymmetric trimeric fragment {Cu3[RC(S)NP(S)(OiPr)2]3} in
the structure of the polynuclear complexes.
Obviously, the 31P chemical shifts in the [Cu3L3] and [(Cu3L3)2]
aggregates cannot be identical due to unequivalent electronic situ-
ation on the phosphorus nuclei and different environment in a
crystal. The 31P CPMAS NMR spectra containing the only one sets
of signals, that proves the formation of the only type of the com-
plexes in the obtained crystal samples, not the mix of the [Cu3L3]
and [(Cu3L3)2] aggregates.
At the same time, the given method does not allow to distin-
guish the trimeric compounds from the centrosymmetric dimer
of trimers. This example shows that spectral identification of the
structure of polynuclear aggregates in the solid state on the basis
of 31P MAS data should be necessarily supplemented by crystallo-
graphic data and additional information using methods sensitive to
change of a coordination environment of copper(I).
3. Experimental
The X-ray data have shown that complex 2 contains three dif-
ferent types of the phosphorus atoms (the P@S group and two non-
equivalent PPh3 groups). The solid state 31P{1H} CPMAS NMR
spectrum of this compound contains a singlet for the phosphorus
atom of Lꢀ (Table 4). The signals for the phosphorus atoms of the
PPh3 ligands were observed as multiplets owing to the indirect
spin–spin interaction 1J(63,65Cu–31P), and 2J(31P–31P) (Fig. 5). The
presence of both two NMR-active copper isotopes (65Cu and
3.1. Physical measurements
1H and 31P NMR experiments in solutions were performed on a
Bruker AMX-300 NMR spectrometer. 31P NMR spectra with contin-
uous wave 1H decoupling were acquired using a single pulse of
7 ls duration (p/4) and a recycle delay varying between 1 and
5 s to ensure no saturation. 31P solid-state magic angle spinning
(MAS) NMR were carried out on a Bruker Avance 400 (9.4 T) spec-
trometer using a 4 mm probe-head. The 31P{1H} cross-polarization
(CP) MAS NMR spectra were recorded at a spinning frequency of
14 kHz using a ramped cross-polarization [24] with a contact time
of 1 ms and a recycle delay of 2 s. 1H decoupling was achieved
using the SPINAL-64 sequence [25] with a 1H nutation frequency
of about 60 kHz. Quantitative MAS spectra were acquired (with
Table 4
31P isotropic chemical shifts and 1JP–Cu and 2JP–P coupling constants of CuI complexes 1
and 2.
diso (ppm)
1J (63Cu–31P)
1J (65Cu–31P)
2J (31P–31P)
I (%)
1
2
48.7 [CuL]
50.4 [CuL]
50.9 [CuL]
61.5 [CuL]
ꢀ3.0 [PPh3]
ꢀ11.8 [PPh3]
33.0
34.1
32.9
33.4
32.0
34.6
and without 1H decoupling) using single pulse of 0.5
/12) and a recycle delay of 1 s. Chemical shifts are referred to
SiMe4 (1H) and 85% H3PO4 31P) solutions. All MAS NMR spectra
were modeled using the DMFIT program [16]. Infrared spectra
ls duration
(p
1124 Hz
922 Hz
1204 Hz
977 Hz
121 Hz
121 Hz
(

F.D. Sokolov et al. / Journal of Organometallic Chemistry 694 (2009) 167–172
171
A
60
40
20
0
-20
(ppm)
B
C
*
*
experimental
simulation
coupling with63Cu
coupling with 65Cu
}
}
PPh3 site
coupling with63Cu
coupling with 65Cu
PPh3 site #1
ssb
(ppm)
12
8
4
0
-4
-8 -12 -16 -20 -24 -28
Fig. 5. The solid state 31P{1H} CPMAS NMR spectrum of the mononuclear complex [Cu(PPh3)2L] (2) (A). Expansion of the experimental (B) and simulated J-multiplet patterns
(C) of the PPh3 ligands. Spinning side-band is marked with an asterisk ( ).
*
(Nujol) were recorded with a Specord M-80 spectrometer in the
frequency range 400–3600 cmꢀ1. Electrospray ionization mass
spectra were measured with a Finnigan-Mat TCQ 700 mass spec-
trometer on a 10ꢀ6 M solution in CH3OH. The speed of sample sub-
(POC), 561, 567, 589, 637 (P@S) cmꢀ1. ES-MS (positive ion): m/z
(%) = 1643 (20) [Cu5L4]+, 1248 (100) [Cu4L3]+, 853 (12) [Cu3L2]+.
Anal. Calc. for C78H120Cu6N12O12P6S12 (2369.76): C, 39.53; H,
5.10; N, 7.09. Found: C, 39.68; H, 5.03; N, 7.21%.
mission was 2
l
L/min. The ionization energy was 4.5 kV and the
Path b: A suspension of HL (0.996 g, 3 mmol) in aqueous ethanol
(25 mL) was mixed with an ethanol solution of KOH (0.185 g,
3.3 mmol). The resulting mixture was added dropwise to the sus-
pension of Cu(NO3)2 ꢁ 3H2O (0.363 g, 1.5 mmol) in aqueous ethanol
(20 mL). The mixture was stirred at room temperature for 1.5 h.
The obtained precipitate of KNO3 was filtered and the solvent
was then removed in vacuum. The residue was recrystallized from
a dichloromethane/n-hexane mixture 1:5 (v/v). Complex 1 was ob-
tained as light colorless crystals.
capillary temperature was 200 °C. Elemental analyses were per-
formed on a Perkin–Elmer 2400 CHN microanalyser.
3.2. Synthesis of HL
N-(Diisopropoxythiophosphinyl)-N0-phenylthiourea (HL) was
prepared according to the previously described method [12].
3.3. Synthesis of [(Cu3L3)2] (1)
3.4. Synthesis of [Cu(PPh3)2L] (2)
Path a: A suspension of HL (0.996 g, 3 mmol) in aqueous ethanol
(25 mL) was mixed with an ethanol solution of KOH (0.185 g,
3.3 mmol). The resulting mixture was added dropwise to the sus-
pension of CuI (0.570 g, 3 mmol) in aqueous ethanol (20 mL). The
mixture was stirred at room temperature for 1.5 h. The obtained
precipitate of KI was filtered and the solvent was then removed
in vacuum. The residue was recrystallized from a dichlorometh-
ane/n-hexane mixture 1:5 (v/v). Complex 1 was obtained as light
colorless crystals. Yield: 0.782 g, (66%). M.p. 165 °C. 1H NMR
A suspension of HL (0.996 g, 3 mmol) in aqueous ethanol
(25 mL) was mixed with an ethanol solution of KOH (0.185 g
3.3 mmol). A dichloromethane (25 mL) solution of [Cu(PPh3)3I]
(2.931 g, 3 mmol) was added dropwise under vigorous stirring to
the resulting potassium salt. The mixture was stirred at room tem-
perature for a further 1 h and a precipitate was filtered off. The fil-
trate was concentrated until the crystallization began. The residue
was recrystallized from a dichloromethane/n-hexane mixture 1:5
(v/v). Complex 2 was obtained as colorless crystals. Yield: 1.917 g
(87%). M.p. 145 °C (146 °C, Ref. [11]). 1H NMR (CDCl3) 1.28 (d,
3
3
(CDCl3) 1.36 (d, JH,H = 6.1 Hz, 6H, CH3), 1.37 (d, JH,H = 6.1 Hz, 6H,
3
3
CH3), 4.80 (d. sept, JPOCH = 10.6 Hz, JH,H = 6.1 Hz, 2H, OCH), 7.06–
7.11 (m, 1H, p-C6H5), 7.26–7.31 (m, 2H, m-C6H5), 7.59–7.61 (m,
3
3JH,H = 6.2 Hz, 6H, CH3), 1.31 (d, JH,H = 6.1 Hz, 6H, CH3), 4.74 (d.
4
3
3
2H, o-C6H5), 8.46 (d, JPNCNH = 8.2 Hz, 1H, NH) ppm. 31P{1H} NMR
sept, JPOCH = 10.8 Hz, JH,H = 6.2 Hz, 2H, OCH), 7.01–7.06 (m, 1H,
p-C6H5, L), 7.28–7.41 (m, 30H, C6H5), 7.51–7.54 (m, 2H, o-C6H5,
(CDCl3) 50.4 ppm. IR: 3354 (NH), 1500–1530 (SCN), 985, 1020

172
F.D. Sokolov et al. / Journal of Organometallic Chemistry 694 (2009) 167–172
L), 7.64–7.71 (m, 2H, m-C6H5, L) ppm. 31P{1H} NMR (CDCl3) ꢀ1.2 (s,
2P, PPh3), 54.9 (s, 1P, NPS) ppm. IR: 3320 (NH), 1530 (SCN), 976,
995, 1012, 1025 (POC), 606 (P@S) cmꢀ1. ES-MS (positive ion): m/
z (%) = 1248 (12) [Cu4L3]+, 854 (4) [Cu3L2]+, 588 (100) [Cu(PPh3)2]+.
Anal. Calc. for C49H50CuN2O2P3S2 (919.53): C, 64.00; H, 5.48; N,
3.05. Found: C, 63.87; H, 5.56; N, 3.10%.
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. Crystallographic data for
the structural analyses with thermal parameters and complete ta-
bles of interatomic distances and angles. Supplementary data asso-
ciated with this article can be found, in the online version, at
doi:10.1016/j.jorganchem.2008.10.010.
3.5. Crystal structure determination and refinement
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4. Conclusions
The cyclic [Cu3L3] unit is rather common for copper(I) com-
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Acknowledgments
This work was supported by the joint program of CRDF and the
Russian Ministry of Education and Science (BRHE 2008 Y5-C-07-
09); Russian Science Support Foundation.
[29] M.G. Babashkina, R.C. Luckay, D.A. Safin, A. Klein, A.A. Kostin, M. Bolte, T. Pape,
F.D. Sokolov, F.E. Hahn, in preparation.
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M.G. Babashkina, Chem. Comm., submitted for publication.
Appendix A. Supplementary material
CCDC 652056 and 652057 contains the supplementary crystal-
lographic data for this paper. These data can be obtained free of