Synthesis, characterisation and luminescent properties of mixed-ligand copper(I) complexes incorporating N-thiophosphorylated thioureas and phosphane ligands

Article abstract of DOI:10.1002/ejic.201000165

The potassium salts of H₂NC(S)NHP(S)(OiPr)₂ (HL ^I) or o-C₆H₄[NHC(S)NHP(S)(OiPr) ₂]₂ (H₂L^II) react with [Cu(PPh ₃)₃I] or a mixture of C

Full text of DOI:10.1002/ejic.201000165

FULL PAPER
DOI: 10.1002/ejic.201000165
Synthesis, Characterisation and Luminescent Properties of Mixed-Ligand
Copper(I) Complexes Incorporating N-Thiophosphorylated Thioureas and
Phosphane Ligands
Maria G. Babashkina,[a] Damir A. Safin,*[a] Axel Klein,*[a] and Michael Bolte[b]
Keywords: Chelate complexes / Copper / Crystal Structure / Luminescence / Phosphanes / Thiourea
The potassium salts of H2NC(S)NHP(S)(OiPr)2 (HLI) or o-
C6H4[NHC(S)NHP(S)(OiPr)2]2 (H2LII) react with [Cu(PPh3)3I]
or a mixture of CuI and Ph2P(CH2)1–3PPh2 or Ph2P(C5H4-
FeC5H4)PPh2 in aqueous EtOH/CH2Cl2 to give mononuclear
complexes [Cu(PPh3)LI] (1), [Cu{Ph2P(CH2)2PPh2}LI] (2),
[Cu{Ph2P(CH2)3PPh2}LI] (3) or [Cu{Ph2P(C5H4FeC5H4)PPh2}-
LI] (4), or dinuclear complexes [Cu2(Ph2PCH2PPh2)LI2] (5),
[Cu2(PPh3)2LII] (6), [Cu2{Ph2P(CH2)2PPh2}2LII] (7), [Cu2{Ph2P-
(CH2)3PPh2}2LII] (8), [Cu2{Ph2P(C5H4FeC5H4)PPh2}2LII] (9) or
[Cu2(Ph2PCH2PPh2)LII] (10). The structures of these com-
pounds were investigated by 1H and 31P{1H} NMR, UV/Vis
spectroscopy and elemental analysis. The crystal structures
of H2LII, 1, 3–6, 8 and 10 were determined by single-crystal
X-ray diffraction. The luminescent properties of complexes
1–10 in the solid state are reported.
thiourea containing a cyclam fragment with [Cu(PPh3)3I]
lead to the tetranuclear CuI complex [{Cu(PPh3)2}4-
(cyclam)] (Scheme 1).[12]
Introduction
In preceding papers we described heteroligand complexes
of CuI with a number of N-thiophosphorylated thioureas
We have also described a number of N-(thio)phosphoryl-
and thioamide RC(S)NHP(S)(OiPr)2 [R = morpholin-4-yl, ated bis(thio)ureas, which are potentially bridging ligands,
piperidin-1-yl,[1] (1-naphthyl)NH,[2] NH2 (HLI),[1,3] (pyr- and investigated their complexation properties towards
idin-2-yl)NH, (pyridin-3-yl)NH, H2N-6-Py-2-NH,[4] Ph, various metal cations.[6,13–20] Only one dinuclear hetero-
Et2N,[5–7] (EtO)2P(O)CH2C6H4-4-NH,[8] MeNH, iPrNH, ligand complex of CuI with N-thiophosphoryl bis(thio-
tBuNH, Me2N, PhNH,
2,6-Me2C6H3NH, 2,4,6- urea), containing 1,10-diaza-18-crown-6, and PPh3
Me3C6H2NH[9–11] and triphenylphosphane or Ph2P- (Scheme 1) has been described.[6] To the best of our knowl-
]
(CH2)1–3PPh2 and Ph2P(C5H4FeC5H4)PPh2. We also edge there are no crystal structures of such types of com-
showed that the reactions of alkaline salts of the tetrakis- plexes. Furthermore, we have described two CuI complexes
Scheme 1.
[CuPPh3{RC(S)NP(S)(OiPr)2}] (R = H2N-6-Py-2-NH,[4]
[a] Institut für Anorganische Chemie, Universität zu Köln,
(EtO)2P(O)CH2C6H4-4-NH[8]) containing one triphen-
Greinstrasse 6, 50939 Köln, Germany
ylphosphane (PPh3) ligand. A number of heteroligand CuI
Fax: +49-221-4705196
E-mail: damir.safin@ksu.ru
complexes containing both aryl-substituted pnictides and
axel.klein@uni-koeln.de
cyclic thioureas or pyridinethiolates have also been de-
scribed.[21–23] A combination of these two types of ligands
might lead to interesting and unusual photophysical and
electrochemical properties.[24]
[b] Institut für Anorganische Chemie, J.-W.-Goethe-Universität,
60438 Frankfurt/Main,
Germany
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201000165.
View this journal online at
wileyonlinelibrary.com
4018
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 4018–4026

Mixed-Ligand Copper(I) Complexes
In this contribution we describe new heteroligand com-
plexes of CuI with H2NC(S)NHP(S)(OiPr)2 (HLI) and o-
C6H4[NHC(S)NHP(S)(OiPr)2]2 (H2LII; Scheme 2) and
phosphanes [PPh3, Ph2P(CH2)1–3PPh2, Ph2P(C5H4-
FeC5H4)PPh2] along with their structural characterisation
and luminescent properties. Mononuclear derivatives with
non-bridging thiourea ligands and the phosphane ligands
PPh3, Ph2P(CH2)1–3PPh2 or Ph2P(C5H4FeC5H4)PPh2 have
recently been described.[10,11]
Results and Discussion
Synthesis
N-Thiophosphorylated thiourea HLI was prepared as de-
scribed previously.[1,3,25] N-Thiophosphorylated bis(thio-
urea) H2LII was prepared by addition of o-phenylenediamine
to O,OЈ-diisopropylthiophosphoric isothiocyanate, (iPrO)2-
P(S)NCS, similarly to the previously described method.[13]
Reactions of the potassium salts of HLI and H2LII with
[Cu(PPh3)3I] or a mixture of CuI and Ph2P(CH2)1–3PPh2 or
Ph2P(C5H4FeC5H4)PPh2 in aqueous EtOH/CH2Cl2 led to
the mononuclear complexes [Cu(PPh3)LI] (1), [Cu{Ph2P-
(CH2)2PPh2}LI] (2), [Cu{Ph2P(CH2)3PPh2}LI] (3) or
[Cu{Ph2P(C5H4FeC5H4)PPh2}LI] (4), or the dinuclear com-
plexes [Cu2(Ph2PCH2PPh2)LI2] (5), [Cu2(PPh3)2LII] (6),
[Cu2{Ph2P(CH2)2PPh2}2LII] (7), [Cu2{Ph2P(CH2)3PPh2}2-
LII] (8), [Cu2{Ph2P(C5H4FeC5H4)PPh2}2LII] (9) or [Cu2-
(Ph2PCH2PPh2)LII] (10) (Scheme 3).
Scheme 2.
Scheme 3.
Eur. J. Inorg. Chem. 2010, 4018–4026
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M. G. Babashkina, D. A. Safin, A. Klein, M. Bolte
1
FULL PAPER
The complexes obtained are colourless crystalline pow- absent in the H NMR spectra of 1–10. This confirms the
1
ders, soluble in acetone, benzene, CH2Cl2, DMSO and anionic character of the ligands in the complexes. The H
DMF and insoluble in n-hexane. H and 31P{1H} NMR NMR spectra of 2, 3, 5, 7, 8 and 10 contain signals for the
1
spectroscopy indicated that the deprotonated thioureas LI,II CH2 protons of the phosphanes Ph2P(CH2)1–3PPh2 at δ =
are coordinated through the sulfur atoms of the thio- 1.56–2.97 ppm, whereas signals for the C5H4 protons in the
carbonyl and thiophosphoryl groups in all cases.
spectra of 4 and 9 are observed at δ = 4.20–4.29 ppm.
The absorption spectra of the complexes 1–10 were
studied in CH2Cl2 solution (Figure S1 in the Supporting
Information), whereas their luminescent properties were in-
vestigated in the solid state at room temperature (Figure 1).
The data are reported in Table 1. Complexes 2–5 and 7–10
show emission in the solid state. The origin of the emission
is believed to be based on intraligand transitions centred
on the thiophosphoryl component of the ligands, which are
influenced by the nature of the phosphane. PPh3 complexes
did not exhibit any luminescence properties. One interesting
point in this respect is the unusually low energy and inten-
sity of the emission of the complexes 5 and 10, which might
be due to contributions from cluster-centred charge-transfer
transition in these dinuclear aggregates, which show rather
short Cu1···Cu2 distances.
IR and NMR Spectroscopy and Photophysical Properties
The IR spectrum of H2LII contains a weak band centred
at 652 cm–1 assigned to the P=S groups. The S=C–N frag-
ment in the spectrum of the bis(thiourea) is shown as a
band at 1553 cm–1. There are two absorption bands at 3204
and 3422 cm–1 corresponding to the NH groups in the spec-
trum of H2LII, whereas a unique band at 3348–3369 cm–1
related to the (aryl)NH group is observed in the spectra of
6–10. The IR spectra of the complexes contain a band at
594–616 cm–1 for the P=S group of the anionic forms LI,II
.
These bands are shifted to low frequencies relative to the
parent ligands as a result of coordination to the CuI ion. In
the IR spectra of 1–10 there are bands at 1537–1562 cm–1
corresponding to the conjugated SCN fragment. In the IR
spectra of 1–5 there are also a number of bands at 1609–
1629, 3120–3137, 3241–3261 and 3483–3501 cm–1 corre-
sponding to the NH2 group. In addition, there is a broad
intense band arising from the POC group at 988–1014 cm–1
in the spectra of H2LII and the complexes.
In the 31P{1H} NMR spectra of the complexes, the reso-
nances in the range δ = 54.4–58.7 ppm correspond to the
phosphorus atom of the thiophosphoryl group. These sig-
nals are shifted downfield relative to those in the spectra of
HLI and H2LII. The signals of the phosphorus atoms of
PPh3 in the spectra of the complexes 1 and 6 are found at
δ = 0.4 and –1.5 ppm, respectively, whereas the signals for
the phosphane phosphorus atoms in the 31P{1H} NMR
spectra of the complexes 2–5 and 7–10 exhibit chemical
shifts from δ = –22.4 to –10.6 ppm.
Figure 1. Emission spectra of 2, 3, 4 and 5. The spectra of 7–10
are similar to the spectra of 2–5, respectively. The excitation wave-
length was chosen from the λmax of the absorption.
1
The H NMR spectra of H2LII and 1–10 contain only
signals that correspond to the proposed structures. The
spectra contain a set of signals for the iPr protons: signals
for the CH3 protons at δ = 0.85–1.47 ppm and signals for
the CH protons at δ = 4.27–4.89 ppm. The signals for the
aromatic ring and (aryl)NH protons are observed at δ =
Crystal Structures
6.70–8.29 ppm. Signals of the NH2 group in the spectra of
Crystals of H2LII, 1, 3–6, 8 and 10 were obtained by slow
1
1–5 are observed at δ = 5.33–5.72 ppm. In the H NMR evaporation of the solvent from their solutions in acetone/n-
spectrum of H2LII the signal for the NHP proton is found hexane (1) or CH2Cl2/n-hexane mixtures (1:5, v/v; see Exp.
at δ = 9.12 ppm. The signals for the NHP group proton are Sect.). The molecular structures of H2LII, 1, 3, 4, 5, 6, 8 and
Table 1. UV/Vis absorption and emission maxima for complexes 1–10.[a]
Complex
λabs [nm] (ε [dm3 mol–1 cm–1])
λem [nm]
Complex
λabs [nm] (ε [dm3 mol–1 cm–1])
λem [nm]
1
2
3
4
5
310 (10221)
no emission
478
6
7
304 (17631)
no emission
473
254 (19853), 302 (9632)
250 (19122), 307 (9471)
247 (19390), 310 (9718)
252 (3529), 373 (13382)
247 (31269), 306 (17564)
253 (28113), 306 (18103)
259 (33728), 311 (20824)
255 (3602), 379 (13127)
472
483
508
8
470
486
513
9
10
[a] Emission data obtained with excitation at λ of the long-wavelength absorption. The absorption spectra of the corresponding potassium
salts show weak absorption bands at 289 (ε = 172 dm3 mol–1 cm–1) (KLI) and 297 nm (ε = 238 dm3 mol–1 cm–1) (K2LII).
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Eur. J. Inorg. Chem. 2010, 4018–4026

Mixed-Ligand Copper(I) Complexes
10 are shown in Figures 2, 3, 4, 5, 6, 7, 8, and 9, respectively.
Selected bond lengths and angles are given in Tables 2 and
3.
Figure 5. Thermal-ellipsoid representation of the independent mo-
lecule A of 4 (hydrogen atoms have been omitted for clarity). Ellip-
soids are drawn at the 30% probability level.
Figure 2. Thermal-ellipsoid representation of H2LII (hydrogen
atoms have been omitted for clarity). Ellipsoids are drawn at the
30% probability level.
Figure 6. Thermal-ellipsoid representation of 5 (hydrogen atoms
have been omitted for clarity). Ellipsoids are drawn at the 30%
probability level.
Figure 3. Thermal-ellipsoid representation of 1 (hydrogen atoms
have been omitted for clarity). Ellipsoids are drawn at the 30%
probability level.
Figure 7. Thermal-ellipsoid representation of 6 (hydrogen atoms
have been omitted for clarity). Ellipsoids are drawn at the 30%
probability level.
an anti disposition relative to the phenylene spacer. Intra-
and intermolecular hydrogen bonds of the type N–H···O–P
and N–H···S=C, respectively, are present in the crystal of
H2LII (Table 4). Intramolecular hydrogen bonds are formed
between the oxygen atoms of the P–O groups and the hy-
drogen atoms of the (aryl)NH fragments, which in turn
leads to an (E,E) conformation of the SCNP backbones.
Figure 4. Thermal-ellipsoid representation of 3 (hydrogen atoms
have been omitted for clarity). Ellipsoids are drawn at the 30%
probability level.
The bis(thiourea) H2LII crystallises in the monoclinic Intermolecular hydrogen bonds are formed between the hy-
space group C2/c. The parameters of the C=S, C–N, P–N drogen atom of one PNH group and the sulfur atom of
and P=S bonds observed for H2LII (Table 2) are in the the C=S group, and the same types of atoms of the two
range typical for N-thiophosphorylated thiourea deriva- neighbouring molecules. As a result of the intermolecular
tives.[14] The two NC(S)N moieties show significant planar- hydrogen bonds (Table 4) a polymeric chain is formed in
ity (Figure 2). The two chelate backbones C(S)NP(S) are in the crystal of H2LII.
Eur. J. Inorg. Chem. 2010, 4018–4026
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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4021

M. G. Babashkina, D. A. Safin, A. Klein, M. Bolte
FULL PAPER
Note that in our recent publication we published the syn-
thesis of the complex [Cu(PPh3)2LI] (11), which contains
two PPh3 ligands.[1] Efforts to recrystallise 11 from a
CH2Cl2/n-hexane mixture did not lead to crystals suitable
for X-ray analysis, but according to the NMR spectroscopic
data and elemental analysis, the material still contains two
PPh3 ligands. In the course of this work we tried to obtain
crystals by the recrystallisation of 11 from an acetone/n-
hexane mixture. Surprisingly, according to the NMR spec-
troscopic data and elemental analysis, the crystals obtained
(suitable for X-ray diffraction) have the composition
[Cu(PPh3)LI] (1).
In the structure of 1 the geometry around the Cu atom
is trigonal, formed by two S atoms and one PPh3 ligand
(Figure 3). The Cu–P bond [2.2127(7) Å, Table 2] is of prac-
tically the same length as observed for the complexes
[CuPPh3{RC(S)NP(S)(OiPr)2}] [R = H2N-6-Py-2-NH,[4]
(EtO)2P(O)CH2C6H4-4-NH[8]] with trigonally coordinated
CuI. The six-membered CuSPNCS metallocycle has the
conformation of a distorted boat. The fragment NC(S)NP
is almost planar with the sulfur atom of the thiophosphoryl
group deviating significantly from the average plane of this
fragment; the torsion angle S1–P1–N1–C1 is 49.1(3)°.
In the structures of 3 and 4 the CuI cation is in a P2S2
tetrahedral environment formed by the two sulfur atoms of
the deprotonated thiourea LI ligand and the two phospho-
rus atoms of the Ph2P(CH2)3PPh2 or Ph2P(C5H4FeC5H4)-
PPh2 molecule, respectively (Figures 4 and 5). The asym-
metric unit of 4 contains two independent molecules. The
Cu–S(C), Cu–S(P) and Cu–P bonds in 3 and 4 are markedly
longer than those in 1 (Table 2). The S–Cu–S angle in 3 and
Figure 8. Thermal-ellipsoid representation 8 (hydrogen atoms have
been omitted for clarity). Ellipsoids are drawn at the 30% prob-
ability level.
Figure 9. Thermal-ellipsoid representation of 10 (hydrogen atoms
have been omitted for clarity). Ellipsoids are drawn at the 30%
probability level.
Table 2. Selected bond lengths [Å] and angles [°] for H2LII, 1, 3, and 4.
H2LII
1
3
4
C=S
P=S
P–N
P–O
1.6737(15), 1.6806(16)
1.9133(6), 1.9162(6)
1.6775(14), 1.6838(14)
1.5733(12), 1.5797(13),
1.5804(14), 1.5805(12)
1.377(2)
1.752(3)
1.9594(9), 2.121(5)
1.603(2)
1.738(2)
1.9831(9)
1.602(2)
1.588(2), 1.589(2)
1.730(9), 1.738(11)[a]
1.987(3), 1.976(3)[a]
1.610(7), 1.609(7)[a]
1.593(6), 1.594(6),
1.578(2), 1.582(2)
1.578(6),[a] 1.583(6)[a]
1.316(10), 1.312(11)[a]
1.343(11), 1.356(12)[a]
2.325(3), 2.329(3)[a]
2.385(2), 2.358(2)[a]
2.280(2), 2.314(2),
C–N(P)
C–N
Cu–S
Cu–S(P)
Cu–P
1.314(3)
1.338(3)
2.2018(7)
2.2463(8), 2.376(5)
2.2127(7)
1.333(3)
1.335(3)
2.3245(7)
2.3559(6)
1.340(2), 1.343(2)
2.2799(6), 2.2836(6)
2.296(2),[a] 2.300(2)[a]
116.2(6), 115.8(6)[a]
127.1(7), 127.5(8)[a]
116.6(8), 116.6(9)[a]
125.3(6), 125.1(7)[a]
119.1(3), 118.2(3)[a]
106.21(9), 107.54(9)[a]
110.68(9), 109.86(9)[a]
104.22(9), 110.22(9),
101.70(9),[a] 116.24(9)[a]
121.81(3), 124.53(3)[b]
S–C–N
122.21(12), 122.93(12)
120.61(12), 121.32(12)
116.44(14), 116.46(13)
127.93(12), 128.32(12)
111.12(6), 111.86(6)
115.0(2)
129.0(2)
116.0(2)
130.7(2)
109.5(2), 121.94(9)
110.52(13), 115.86(3)
117.5(2)
127.1(2)
115.4(2)
124.9(2)
118.52(8)
106.72(2)
99.62(2)
S–C–N(P)
N–C–N
C–N–P
N–P–S
S–Cu–S
P–Cu–P
P–Cu–S
127.29(3)
107.96(2), 110.53(2)
P–Cu–S(P)
116.76(3), 121.15(12)
113.35(2), 118.27(2)
105.55(8), 118.87(9),
104.40(8),[a] 115.58(9)[a]
103.6(3), 108.5(3)[a]
97.10(11), 93.08(11)[a]
Cu–S–C
Cu–S–P
Cu–S–Cu
107.21(8)
86.9(2), 94.65(3)
106.88(9)
96.90(3)
104.30(9), 99.72(9)[b]
98.38(3), 97.74(4)[b]
73.38(2), 69.95(2)
[a] Data for two independent molecules A and B. [b] Data for the Cu2–S4–C2(N4)–N3–P2(O3)(O4)–S3 backbone.
4022 Eur. J. Inorg. Chem. 2010, 4018–4026
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Mixed-Ligand Copper(I) Complexes
Table 3. Selected bond lengths [Å] and angles [°] for 5, 6, 8, and 10.
5
6
8
10
C=S
P=S
P–N
P–O
1.769(3), 1.756(3)[a]
1.9934(10), 1.9917(10)[a]
1.617(2), 1.613(2)[a]
1.577(2), 1.583(2),
1.724(3), 1.733(3)
1.9772(10), 1.9837(11)
1.606(2), 1.624(2)
1.570(2), 1.576(2),
1.583(2)
1.315(4), 1.318(4)
1.355(4), 1.370(4)
2.3124(8), 2.3437(8)
1.735(3), 1.741(3)
1.9759(10), 1.9765(10)
1.615(2), 1.622(2)
1.571(2), 1.580(2),
1.5879(19), 1.590(2)
1.318(4), 1.325(4)
1.358(3), 1.360(4)
2.3002(8), 2.3429(8)
1.751(6), 1.774(5)
1.987(2), 1.988(2)
1.598(5), 1.599(5)
1.571(4), 1.574(4),
1.583(4), 1.584(4)
1.296(7), 1.313(8)
1.347(8), 1.350(8)
2.3845(13), 2.4164(16),
2.4204(14), 2.5020(17)
2.3327(16), 2.3371(17)
2.2277(16), 2.2355(15)
1.576(2),[a] 1.584(2)[a]
1.326(3), 1.311(4)[a]
1.324(4), 1.346(4)[a]
2.3122(7), 2.5598(7),
2.3799(7),[a] 2.4309(7)[a]
2.3236(7), 2.3250(8)[a]
2.2364(7), 2.2422(7)[a]
C–N(P)
C–N
Cu–S
Cu–S(P)
Cu–P
2.3618(8), 2.3812(8)
2.2756(9), 2.2960(8),
2.3121(8), 2.3155(9)
114.4(2), 114.5(2)
127.7(2)
117.8(3), 117.9(3)
125.4(2), 125.5(2)
117.78(10), 119.41(10)
103.26(3), 104.27(3)
2.2967(8), 2.3429(8)
2.2472(8), 2.2593(8),
2.2702(8), 2.2808(9)
114.0(2), 115.2(2)
127.1(2), 127.6(2)
117.7(2), 118.4(3)
123.3(2), 126.5(2)
116.46(9), 119.65(10)
108.57(3), 110.49(3)
S–C–N
S–C–N(P)
N–C–N
C–N–P
N–P–S
116.2(2), 115.3(2)[a]
125.9(2), 127.0(2)[a]
117.8(2), 117.6(3)[a]
124.6(2), 125.8(2)[a]
118.55(9), 116.80(9)[a]
98.10(2), 106.57(3),
108.96(2), 99.92(2),[a]
107.24(3),[a] 107.34(3)[a]
117.0(5), 117.2(4)
125.3(5), 126.2(5)
116.8(5), 117.5(5)
127.4(4), 128.5(4)
113.9(2), 115.19(19)
99.15(5), 100.57(5),
106.23(6), 115.15(6)
S–Cu–S
P–Cu–P
P–Cu–S
111.18(3), 121.11(3)
101.07(3), 105.63(3),
106.95(3), 121.47(3)
101.19(3), 105.98(3),
113.02(3), 116.46(3)
102.64(10), 102.84(10)
97.90(3), 99.81(3)
122.16(3), 103.03(3)[a]
116.76(3), 121.15(12)
107.21(8)
102.05(3), 103.03(3),
107.53(3), 112.21(3)
107.17(3), 115.21(3),
123.04(3), 123.66(3)
102.28(9), 104.29(9)
98.28(6), 104.58(5),
114.95(6), 120.35(6)
116.22(6), 120.18(6)
P–Cu–S(P)
Cu–S–C
93.50(17), 95.03(17),
107.7(2), 107.92(19)
99.25(8), 99.85(7)
68.27(4), 70.27(4)
Cu–S–P
Cu–S–Cu
86.9(2), 94.65(3)
99.39(4), 102.05(4)
94.73(4), 95.81(4)
[a] Data for the Cu2–S4–C2(N4)–N3–P2(O3)(O4)–S3 backbone.
Table 4. Hydrogen-bond lengths [Å] and angles [°] for H2LII, 1, 3,
4, 5, 6, 8, and 10.
In the dinuclear complex 5 the Ph2PCH2PPh2 ligand
bridges two CuI ions with two deprotonated thiourea
groups coordinated to the Cu atoms through the thiophos-
phoryl and thiocarbonyl sulfur atoms of the ligand, the lat-
ter acting as a (µ,η1,η1)-Cu–S–Cu bridge, thus forming a
dinuclear entity (Figure 6). Both CuI atoms in 5 are in a
tetrahedral PS3 environment. The same type of anionic
thiourea ligand was observed in the structure of poly-
nuclear CuI complexes.[1,3,7,9–11] The Cu1···Cu2 distance
of 2.8355(4) Å is slightly longer than the sum of two
van der Waals radii of CuI (2.80 Å).[26]
D–H···A
D–H
H···A
D···A
D–H···A
H2LII[a] N1–H1···S2#1
N2–H2···O2
0.79(2) 2.57(2) 3.3441(15) 170.0(18)
0.83(2) 2.31(2) 2.9644(17) 135.9(19)
0.81(2) 2.56(2) 3.3286(16) 158(2)
0.87(2) 2.22(3) 2.8957(18) 134(2)
N3–H3···S4#2
N4–H4···O3
1[b]
3[c]
4[d]
5[e]
N2–H2A···N1#1
N2–H2A···O2#1
N2–H2B···N1#1
N2–H2B···O1#1
N2–H2A···N1#1
0.89(3) 2.23(3) 3.115(3)
0.89(4) 2.47(3) 2.999(3)
0.86(3) 2.37(3) 3.222(3)
0.86(3) 2.53(3) 3.099(3)
172(3)
118(3)
172(2)
124(3)
172.4
0.88
2.10
2.34
2.978(10)
3.166(11)
N2A–H2AA···N1A#2 0.88
156.4
In the crystal, two molecules of the complexes 1 and 3–
5 form centrosymmetric dimers as a result of intermolecular
hydrogen bonds (Table 4). These intermolecular hydrogen
bonds are formed by the hydrogen atom of the NH group
and the nitrogen or oxygen (1 and 3) or solely nitrogen (4
and 5) atoms of the N–P–OiPr group of a further molecule.
In the crystal of 5 there are also intramolecular hydrogen
bonds formed by the NH hydrogen atom of one molecule
of LI and the P=S sulfur atom of a second molecule of LI
(Table 4).
N2–H2A···S3
N2–H2B···N1#1
N4–H4B···S1
N3–H3···N2
N4–H4···Cl11#1
N3–H3···S3
0.86(3) 2.72(3) 3.503(3)
0.94(4) 2.32(4) 3.244(3)
0.83(4) 2.85(4) 3.561(3)
0.69(3) 2.26(3) 2.851(4)
0.77(4) 2.69(4) 3.437(4)
0.85(6) 2.72(6) 3.535(6)
0.84(2) 2.83(3) 3.628(2)
0.86(2) 2.15(3) 2.842(3)
153(3)
167(3)
145(4)
144(4)
164(4)
161(5)
158(3)
137(3)
6[f]
8
10[g]
N3–H3···S2#1
N4–H4···N1
[a] Symmetry codes: #1: –x + 1, y, –z + 3/2; #2: –x + 1, –y + 1,
–z + 1. [b] Symmetry codes: #1: –x + 1, –y, –z. [c] Symmetry codes:
#1: –x + 1, –y, –z + 1. [d] Symmetry codes: #1: –x + 1, –y + 1,
–z. [e] Symmetry codes: #1: –x + 1, –y + 1, –z + 1; #2: –x + 1,
–y + 1, –z + 2. [f] Symmetry codes: #1: –x + 1, –y + 1, –z + 1. [g]
Symmetry codes: #1: –x + 1, –y + 2, –z + 1.
In the structures of 6 and 8, each CuI cation is in a P2S2
tetrahedral environment formed by two sulfur atoms of the
deprotonated N-thiophosphoryl bis(thiourea) LII and two
phosphorus atoms of two PPh3 ligands (6) or one
4 is significantly smaller than that in 1. The P–Cu–P angle Ph2P(CH2)3PPh2 ligand (8; Figures 7 and 8). The Cu–S(C),
in 4 is significantly larger than in 3 (Table 2), as expected Cu–S(P) and Cu–P bonds (Table 3) in 6 and 8 are similar
for the replacement of the flexible –(CH2)3– group by the to those found in the mononuclear analogues.[1–12] The S–
ferrocenediyl unit.
Cu–S angles in 8 are significantly larger than those in 6,
Eur. J. Inorg. Chem. 2010, 4018–4026
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4023

M. G. Babashkina, D. A. Safin, A. Klein, M. Bolte
FULL PAPER
CH2Cl2 were measured with a Lambda-35 spectrometer. Fluores-
cence was measured with a Spex FluoroMax-3 spectrofluorimeter
on solid samples at room temperature. Elemental analyses were
performed with a CHNS HEKAtech EuroEA 3000 analyser.
whereas the P–Cu–P angles in 8 are smaller than those in 6
(Table 3). In the crystals of 6 and 8 an intramolecular hy-
drogen bond is formed by the NH hydrogen atom of one
pendant arm of LII and the NPS nitrogen atom of the sec-
ond pendant arm (Table 4). The second NH hydrogen atom
of LII forms an intermolecular hydrogen bond with the
chlorine atom of a CH2Cl2 molecule in the crystal of 6
(Table 4). Two molecules of 8 form a centrosymmetric di-
Syntheses: N-Thiophosphorylated thiourea HLI was prepared ac-
cording to a previously described method.[25]
H2LII: A solution of o-phenylenediamine (0.540 g, 5 mmol) in an-
hydrous CH2Cl2 (15 mL) was treated under vigorous stirring with
mer in the crystal due to intermolecular hydrogen bonds a solution of (iPrO)2P(S)NCS (0.263 g, 1.1 mmol) in the same sol-
between the second NH hydrogen atom of LII and the C=S
vent. The mixture was stirred for 1 h. The solvent was removed in
vacuo, and the product was purified by recrystallisation from a
sulfur atom (Table 4). This type of intermolecular hydrogen
CH2Cl2/n-hexane mixture (1:5, v/v). Yield: 2.758 g (94%). 1H
bonding is typical of mononuclear analogues.[1–12]
NMR: δ = 1.35–1.47 (m, 24 H, CH3, iPr), 4.89 (dsept, 3JH,H = 6.2,
The structure of 10 is similar to that of 5. In the complex
3JP,H = 10.5 Hz, 4 H, OCH), 7.07–7.32 (m, overlapping with the
10, the deprotonated thiourea LII coordinates two CuI
solvent signal, C6H4 + NHP), 9.12 [br. s, 2 H, (aryl)NH] ppm.
atoms, which are also interconnected by two C=S sulfur
atoms, forming an S2Cu2 four-membered ring (Figure 9).
The Ph2PCH2PPh2 ligand also bridges the two CuI atoms,
thus completing a tetrahedral PS3 environment. The
Cu1···Cu2 distance [2.7629(10) Å] is slightly shorter than
the sum of two van der Waals radii of CuI.[26] In the crystal
of 10 there is an intramolecular hydrogen bond formed by
the NH hydrogen atom of the pendant arm and the P=S
sulfur atom of the second pendant arm (Table 4).
It is reasonable to assume that the formation of 5 and 10
is mainly caused by the rather small bite angle of
Ph2PCH2PPh2, which often does not allow for perfect che-
late binding of metal cations and consequently leads to a
bridging coordination, thus forming dinuclear structures[27]
and often even promoting M–M bond formation.[28]
31P{1H} NMR: δ = 53.0 (s) ppm. IR: ν = 652 (P=S), 993, 1003
˜
(POC), 1553 (S=C–N), 3204, 3422 (NH) cm–1. C20H36N4O4P2S4
(586.72): calcd. C 40.94, H 6.18, N 9.55; found C 41.01, H 6.12, N
9.48.
Complex 1: Complex 1 was prepared according to a previously de-
scribed method,[1] but the residue was recrystallised from an ace-
tone/n-hexane mixture (1:5, v/v). 1: Yield: 0.264 g (91%). M.p. 141–
3
142 °C. 1H NMR (CDCl3): δ = 1.30 (d, JH,H = 6.0 Hz, 6 H, CH3,
3
3
iPr), 1.31 (d, JH,H = 6.1 Hz, 6 H, CH3, iPr), 4.75 (dsept, JH,H
=
3
6.0, JP,H = 10.8 Hz, 2 H, OCH), 5.72 (br. s, 2 H, NH2), 7.28–7.51
(m, 15 H, Ph) ppm. 31P{1H} NMR (CDCl3): δ = 0.4 (s, 1 P, PPh3),
54.4 (s, 1 P, NPS) ppm. IR: ν = 601 (P=S), 1008 (POC), 1546
˜
(SCN), 1614, 3127, 3249, 3496 (NH2) cm–1. C25H31CuN2O2P2S2
(581.15): calcd. C 51.67, H 5.38, N 4.82; found C 51.82, H 5.29, N
4.90.
Complexes 2–5: A suspension of HLI (0.128 g, 0.5 mmol) in aque-
ous ethanol (35 mL) was mixed with an ethanol solution of potas-
sium hydroxide (0.031 g, 0.55 mmol). A mixture of CuI (0.095 g,
0.5 mmol) and Ph2P(CH2)nPPh2 (n = 1, 0.192 g; n = 2, 0.199 g; n
= 3, 0.206 g; 0.5 mmol) or Ph2P(C5H4FeC5H4)PPh2 (0.277 g,
0.5 mmol) in CH2Cl2 (25 mL) was heated at reflux for 0.5 h and
then added dropwise under vigorous stirring to the obtained potas-
sium salt. The mixture was stirred for 1 h, and the resulting precipi-
tate of KI was filtered off. The filtrate was concentrated until crys-
tallisation started. Isolated crystals were obtained from a CH2Cl2/
n-hexane mixture (1:5, v/v). 2: Yield: 0.265 g (74%). M.p. 107–
108 °C. 1H NMR (CDCl3): δ = 1.13–1.34 (m, 12 H, CH3, iPr), 2.25
Conclusions
The potassium salts of LI or LII react with [Cu(PPh3)3I]
or a mixture of CuI and Ph2P(CH2)1–3PPh2 or Ph2P-
(C5H4FeC5H4)PPh2 to form mononuclear (1–4) or dinu-
clear (5–10) complexes. Recrystallisation of 1 from an ace-
tone/n-hexane mixture leads to a complex with one PPh3
molecule, whereas recrystallisation of 1 from a CH2Cl2/n-
hexane mixture gave the product 11 with two PPh3 li-
gands.[1] The formation of dinuclear complexes 5 and 10 is
favoured by the small bite angle of Ph2PCH2PPh2.
3
3
(br. s, 2 H, CH2), 4.73 (dsept, JH,H = 6.2, JP,H = 10.5 Hz, 2 H,
OCH), 5.70 (br. s, 2 H, NH2), 6.97–7.86 (m, overlapping with the
solvent signal, Ph) ppm. 31P{1H} NMR (CDCl3): δ = –12.4 (br. s,
2 P, PPh ), 56.8 (s, 1 P, NPS) ppm. IR: ν = 607 (P=S), 1011 (POC),
˜
2
Complexes 2–5 and 7–10 exhibit emission in the solid
state at ambient temperature, which can be assigned to
1557 (SCN), 1611, 3120, 3241, 3491 (NH2) cm–1. C33H40CuN2-
O2P3S2 (717.28): calcd. C 55.26, H 5.62, N 3.91; found C 55.10, H
5.68, N 3.97. 3: Yield: 0.314 g (86%). M.p. 92–93 °C. 1H NMR
(CDCl3): δ = 1.15 (d, 3JH,H = 6.2 Hz, 6 H, CH3, iPr), 1.18 (d, 3JH,H
= 6.1 Hz, 6 H, CH3, iPr), 1.56–1.97 (m, 2 H, CH2), 2.36 (br. s, 4
3
3ILCT (or MLCT) transitions. In contrast, 1 and 6 fail to
emit under these conditions, probably due to fast relax-
ation.
3
3
H, CH2), 4.67 (dsept, JH,H = 6.1, JP,H = 10.7 Hz, 2 H, OCH),
5.51 (br. s, 2 H, NH2), 6.96–7.83 (m, overlapping with the solvent
signal, Ph) ppm. 31P{1H} NMR (CDCl3): δ = –19.8 (br. s, 2 P,
Experimental Section
PPh ), 58.0 (s, 1 P, NPS) ppm. IR: ν = 610 (P=S), 1004 (POC), 1558
˜
2
Physical Measurements: Infrared spectra were recorded with a
Bruker IFS66νS spectrometer in the range 400–3600 cm–1. NMR
(SCN), 1621, 3132, 3258, 3501 (NH2) cm–1. C34H42CuN2O2P3S2
(731.31): calcd. C 55.84, H 5.79, N 3.83; found C 55.68, H 5.84, N
3.78. 4: Yield: 0.345 g (79%). M.p. 174–175 °C. 1H NMR (CDCl3):
spectra were obtained with a Bruker Avance 300 MHz spectrometer
at 25 °C. H and 31P{1H} NMR spectra (CDCl3) were recorded at δ = 1.19 (t, 3JH,H = 6.0 Hz, 12 H, CH3, iPr), 4.20 (br. s, 4 H, C5H4),
1
3
3
299.948 and 121.420 MHz, respectively. Chemical shifts are re-
ported with reference to SiMe4 (1H) and H3PO4 (31P{1H}). Ab-
sorption spectra of 10–4  (1–5) or 10–5  (6–10) solutions in
4.29 (br. s, 4 H, C5H4), 4.69 (dsept, JH,H = 6.2, JP,H = 10.3 Hz, 2
H, OCH), 5.33 (br. s, 2 H, NH2), 7.21–7.76 (m, overlapping with
the solvent signal, Ph) ppm. 31P{1H} NMR (CDCl3): δ = –17.6 (br.
4024
www.eurjic.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 4018–4026

Mixed-Ligand Copper(I) Complexes
s, 2 P, PPh ), 58.7 (s, 1 P, NPS) ppm. IR: ν = 612 (P=S), 996 (POC),
lapping with the solvent signal, C6H4 + Ph), 8.29 [d, 4JP,H = 9.2 Hz,
2 H, (aryl)NH] ppm. 31P{1H} NMR: δ = –22.4 (s, 2 P, PPh2), 54.9
˜
2
1553 (SCN), 1609, 3137, 3261, 3488 (NH2) cm–1. C41H44CuFeN2-
O2P3S2 (873.25): calcd. C 56.39, H 5.08, N 3.21; found C 56.54, H
(s, 2 P, NPS) ppm. IR: ν = 610 (P=S), 988 (POC), 1537, 1559
˜
1
4.99, N 3.26. 5: Yield: 0.245 g (96%). M.p. 167–168 °C. H NMR (SCN), 3369 (NH) cm–1. C45H56Cu2N4O4P4S4 (1096.19): calcd. C
3
(CDCl3): δ = 1.23 (d, JH,H = 6.2 Hz, 24 H, CH3, iPr), 2.90 (br. s, 49.31, H 5.15, N 5.11; found C 49.48, H 5.06, N 5.18.
3
3
4 H, CH2), 4.64 (dsept, JH,H = 6.1, JP,H = 10.5 Hz, 4 H, OCH),
5.68 (br. s, 4 H, NH2), 6.76–7.74 (m, overlapping with the solvent
signal, Ph) ppm. 31P{1H} NMR (CDCl3): δ = –10.6 (br. s, 2 P,
Crystal Structure Determination and Refinement for H2LII, 1, 3–6,
8, 10: The X-ray diffraction data for crystals of H2LII, 1, 3–6, 8
and 10 were collected with a STOE IPDS-II diffractometer. The
images were indexed, integrated and scaled by using the X-Area
package.[29] Data were corrected for absorption by using the PLA-
TON[30] program. The structures were solved by direct methods
using the SHELXS[31] program and refined first isotropically and
then anisotropically using SHELXL97.[31] Hydrogen atoms were
revealed from ∆ρ maps and those bonded to C were refined by
using a riding model. Hydrogen atoms bonded to N were freely
refined in H2LII, 6 and 8. In 10, U(H) values were set to 1.2Ueq(N),
and N–H distances were restrained to 0.90(3) Å. All figures were
generated by using the Mercury program.[32] CCDC-746321
(H2LII), -742126 (1), -742127 (3), -742128 (4), -742129 (5), -746318
(6), -746320 (8) and -746319 (10) contain the supplementary crys-
tallographic data for this paper. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via
PPh ), 57.3 (s, 2 P, NPS) ppm. IR: ν = 616 (P=S), 994, 1013 (POC),
˜
2
1538, 1562 (SCN), 1629, 3136, 3255, 3483 (NH2) cm–1. C39H54Cu2-
N4O4P4S4 (1022.11): calcd. C 45.83, H 5.33, N 5.48; found C 46.04,
H 5.27, N 5.42.
Complex 6: A suspension of H2LII (0.293 g, 0.5 mmol) in aqueous
ethanol (35 mL) was mixed with an ethanol solution of potassium
hydroxide (0.062 g, 1.1 mmol). A solution of [Cu(PPh3)3I] (0.977 g,
1.0 mmol) in CH2Cl2 (25 mL) was added dropwise to the obtained
potassium salt under vigorous stirring. The mixture was stirred for
1 h, and the resulting precipitate of KI was filtered off. The filtrate
was concentrated until crystallisation started. Isolated crystals were
obtained from a CH2Cl2/n-hexane mixture (1:5, v/v). Yield: 0.880 g
3
(86%). 1H NMR: δ = 1.19 (d, JH,H = 6.1 Hz, 12 H, CH3, iPr),
3
3
1.23 (d, JH,H = 6.1 Hz, 12 H, CH3, iPr), 4.75 (dsept, JH,H = 6.2,
3JP,H = 10.7 Hz, 4 H, OCH), 6.98–7.10 (m, 2 H, C6H4), 7.28–7.47 www.ccdc.cam.ac.uk/data_request/cif. H2LII: C20H36N4O4P2S4, Mr
4
(m, 60 H, Ph), 7.58–7.70 (m, 2 H, C6H4), 7.77 [d, JP,H = 8.1 Hz,
= 586.71, monoclinic, space group C2/c, a = 20.9638(11), b =
11.7659(5), c = 25.9717(15) Å, β = 110.682(4)°, V = 5993.3(5) Å3,
Z = 8, ρ = 1.300 gcm–3, µ(Mo-Kα) = 0.455 mm–1, reflections: 18620
collected, 5240 unique, Rint = 0.0527, R1(all) = 0.0368, wR2(all) =
0.0847. 1: C25H31CuN2O2P2S2, Mr = 581.12, monoclinic, space
group P21/n, a = 18.5869(14), b = 8.3540(8), c = 19.9721(15) Å, β
= 115.697(5)°, V = 2794.5(4) Å3, Z = 4, ρ = 1.381 gcm–3, µ(Mo-
2 H, (aryl)NH] ppm. 31P{1H} NMR: δ = –1.5 (s, 4 P, PPh3), 54.4
(s, 2 P, NPS) ppm. IR: ν = 597 (P=S), 995 (POC), 1540 (SCN),
˜
3348 (NH) cm–1. C92H94Cu2N4O4P6S4 (1760.96): calcd. C 62.75, H
5.38, N 3.18; found C 62.58, H 5.27, N 3.25.
Complexes 7–10: A suspension of H2LII (0.293 g, 0.5 mmol) in
aqueous ethanol (35 mL) was mixed with an ethanol solution of
potassium hydroxide (0.062 g, 1.1 mmol). A mixture of CuI (0.19 g,
1.0 mmol) and Ph2P(CH2)nPPh2 (n = 1, 0.384 g; n = 2, 0.398 g; n
= 3, 0.412 g; 1.0 mmol) or Ph2P(C5H4FeC5H4)PPh2 (0.554 g,
1.0 mmol) in CH2Cl2 (25 mL) was heated at reflux for 0.5 h and
then added dropwise to the obtained potassium salt under vigorous
stirring. The mixture was stirred for 1 h, and the precipitate was
filtered off. The filtrate was concentrated until crystallisation
started. Isolated crystals were obtained from a CH2Cl2/n-hexane
Kα) = 1.070 mm–1, reflections: 36121 collected, 5191 unique, Rint
=
0.0710, R1(all) = 0.0534, wR2(all) = 0.0709. 3: C34H42CuN2O2P3S2,
Mr = 731.27, monoclinic, space group P21/n, a = 16.4108(6), b =
12.2076(4), c = 20.0240(6) Å, β = 100.177(3)°, V = 3948.4(2) Å3, Z
= 4, ρ = 1.230 gcm–3, µ(Mo-Kα) = 0.810 mm–1, reflections: 20673
collected, 7208 unique, Rint = 0.0526, R1(all) = 0.0483, wR2(all) =
0.0873. 4: C41H44CuFeN2O2P3S2, Mr = 873.20, triclinic, space
¯
group P1, a = 11.5630(8), b = 19.9018(14), c = 22.1295(13) Å, α =
116.568(5), β = 99.682(5), γ = 90.364(5)°, V = 4470.7(5) Å3, Z = 4,
ρ = 1.297 gcm–3, µ(Mo-Kα) = 1.035 mm–1, reflections: 36215 col-
lected, 15725 unique, Rint = 0.1939, R1(all) = 0.1530, wR2(all) =
0.1990. 5: C39H54Cu2N4O4P4S4, Mr = 1022.06, monoclinic, space
group P21/c, a = 13.1707(5), b = 32.2392(13), c = 11.1962(4) Å,
β = 98.891(3)°, V = 4696.9(3) Å3, Z = 4, ρ = 1.445 gcm–3,
µ(Mo-Kα) = 1.262 mm–1, reflections: 22460 collected, 8202 unique,
1
mixture (1:5, v/v). 7: Yield: 0.671 g (89%). H NMR: δ = 1.04 (br.
3
s, 12 H, CH3, iPr), 1.14 (d, JH,H = 6.2 Hz, 12 H, CH3, iPr), 2.24
(br. s, 4 H, CH2), 4.59 (br. s, 4 H, OCH), 6.76–7.98 [m, overlapping
with the solvent signal, C6H4 + Ph + (aryl)NH] ppm. 31P{1H}
NMR: δ = –13.2 (br. s, 4 P, PPh ), 56.9 (s, 2 P, NPS) ppm. IR: ν
˜
2
=
594 (P=S), 1006 (POC), 1551 (SCN), 3362 (NH) cm–1.
C72H82Cu2N4O4P6S4 (1508.64): calcd. C 57.32, H 5.48, N 3.71;
Rint
= 0.0490, R1(all) = 0.0459, wR2(all) = 0.0686. 6:
1
found C 57.51, H 5.40, N 3.76. 8: Yield: 0.561 g (73%). H NMR:
C92H94Cu2N4O4P6S4·2CH2Cl2, Mr = 1930.70, triclinic, space group
3
3
δ = 1.09 (d, JH,H = 6.0 Hz, 12 H, CH3, iPr), 1.18 (d, JH,H
=
¯
P1, a = 13.4500(5), b = 17.3046(7), c = 22.2429(8) Å, α = 74.416(3),
6.0 Hz, 12 H, CH3, iPr), 1.81 (br. s, 4 H, CH2), 2.33 (br. s, 8 H,
β = 85.214(3), γ = 70.672(3)°, V = 4705.5(3) Å3, Z = 2, ρ =
1.363 gcm–3, µ(Mo-Kα) = 0.808 mm–1, reflections: 50169 collected,
17546 unique, Rint = 0.0446, R1(all) = 0.0639, wR2(all) = 0.1201.
8: C74H86Cu2N4O4P6S4·CH2Cl2, Mr = 1621.53, triclinic, space
3
3
CH2), 4.63 (dsept, JH,H = 6.1, JP,H = 10.6 Hz, 4 H, OCH), 6.81–
7.70 [m, overlapping with the solvent signal, C6H4 + Ph + (aryl)-
NH] ppm. 31P{1H} NMR: δ = –20.2 (br. s, 4 P, PPh2), 56.6 (s, 2 P,
NPS) ppm. IR: ν = 601 (P=S), 991 (POC), 1548 (SCN), 3353 (NH)
˜
¯
group P1, a = 13.1235(5), b = 18.1183(6), c = 19.0561(7) Å, α =
cm–1. C74H86Cu2N4O4P6S4 (1536.70): calcd. C 57.84, H 5.64, N
69.187(3), β = 74.416(3), γ = 69.245(3)°, V = 3907.4(2) Å3, Z = 2,
ρ = 1.378 gcm–3, µ(Mo-Kα) = 0.892 mm–1, reflections: 68964 col-
lected, 14595 unique, Rint = 0.0605, R1(all) = 0.0584, wR2(all) =
0.1125. 10: C45H56Cu2N4O4P4S4, Mr = 1096.14, monoclinic, space
group P21/c, a = 13.8418(13), b = 33.901(3), c = 11.1897(10) Å, β
= 98.988(7)°, V = 5186.3(8) Å3, Z = 4, ρ = 1.404 gcm–3, µ(Mo-
1
3.65; found C 57.62, H 5.58, N 3.71. 9: Yield: 0.710 g (78%). H
3
NMR: δ = 1.17 (d, JH,H = 6.1 Hz, 24 H, CH3, iPr), 4.25 (br. s, 16
H, C5H4), 4.65 (br. s, 4 H, OCH), 6.70–7.88 [m, overlapping with
the solvent signal, C6H4 + Ph + (aryl)NH] ppm. 31P{1H} NMR: δ
= –18.1 (br. s, 4 P, PPh ), 58.1 (s, 2 P, NPS) ppm. IR: ν = 604
˜
2
(P=S), 1014 (POC), 1552 (SCN), 3367 (NH) cm–1. C88H90Cu2-
Kα) = 1.148 mm–1, reflections: 67245 collected, 9156 unique, Rint
0.1228, R1(all) = 0.1561, wR2(all) = 0.1106.
=
Fe2N4O4P6S4 (1820.58): calcd. C 58.06, H 4.98, N 3.08; found C
58.19, H 4.90, N 3.02. 10: Yield: 0.378 g (69%). 1H NMR: δ = 0.85
3
(br. s, 12 H, CH3, iPr), 1.11 (d, JH,H = 6.2 Hz, 12 H, CH3, iPr), Supporting Information (see footnote on the first page of this arti-
2.97 (br. s, 2 H, CH2), 4.27 (br. s, 4 H, OCH), 7.06–7.38 (m, over-
cle): Absorption spectra of 1–10 in CH2Cl2.
Eur. J. Inorg. Chem. 2010, 4018–4026
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4025

M. G. Babashkina, D. A. Safin, A. Klein, M. Bolte
FULL PAPER
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Received: February 10, 2010
Published Online: July 15, 2010
4026
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 4018–4026