Synthesis, characterization and luminescent properties of heteroligand copper(I) complexes with N-thiophosphorylated thioureas RNHC(S)NHP(S)(OiPr)2 (R = iPr, tBu, Ph, 2,6-Me2C6H3, 2,4,6-Me3C6H2) and phosphines (PPh3, Ph2P(C5H4FeC5H4)PPh2)

Article abstract of DOI:10.1016/j.ica.2010.02.028

Reaction of the potassium salts of RNHC(S)NHP(S)(OiPr)₂ (R = iPr, HL^I; tBu, HL^II; Ph, HL^III; 2,6-Me₂C₆H₃, HL^IV; 2,4,6-Me₃C₆H₂, HL^V) with [Cu(PPh₃)₃I] or a mixture of CuI and Ph₂P(C₅H₄FeC₅H₄)PPh₂ in aqueous EtOH/CH₂Cl₂ leads to mononuclear [Cu(PPh₃)₂L^II] (1), [Cu(PPh₃)₂L^V] (2), [Cu{Ph₂P(C₅H₄FeC₅H₄)PPh₂}L^I] (3), [Cu{Ph₂P(C₅H₄FeC₅H₄)PPh₂}L^II] (4), [Cu{Ph₂P(C₅H₄FeC₅H₄)PPh₂}L^III] (5), [Cu{Ph₂P(C₅H₄FeC₅H₄)PPh₂}L^IV] (6) and [Cu{Ph₂P(C₅H₄FeC₅H₄)PPh₂}L^V] (7) complexes. The structures of these complexes were investigated by ¹H, ³¹P{¹H} NMR spectroscopy and elemental analysis. The crystal structures of 1, 2 and 4 were determined by single crystal X-ray diffraction. The complexes 3-7 exhibit emission in the solid state at ambient temperature that might be explained by the presence of the ferrocene-diyl unit in the chelate phosphine.

Full text of DOI:10.1016/j.ica.2010.02.028

Inorganica Chimica Acta 363 (2010) 1897–1901
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Note
Synthesis, characterization and luminescent properties of heteroligand
copper(I) complexes with N-thiophosphorylated thioureas
RNHC(S)NHP(S)(OiPr)2 (R = iPr, tBu, Ph, 2,6-Me2C6H3, 2,4,6-Me3C6H2)
and phosphines (PPh3, Ph2P(C5H4FeC5H4)PPh2)
a
b
a,
Damir A. Safin a, , Maria G. Babashkina , Michael Bolte , Axel Klein
*
*
a Institut für Anorganische Chemie, Universität zu Köln, Greinstrasse 6, D-50939 Köln, Germany
b Institut für Anorganische Chemie J.-W.-Goethe-Universität, Frankfurt/Main, Germany
a r t i c l e i n f o
a b s t r a c t
Reaction of the potassium salts of RNHC(S)NHP(S)(OiPr)2 (R = iPr, HLI; tBu, HLII; Ph, HLIII; 2,6-Me2C6H3,
HLIV; 2,4,6-Me3C6H2, HLV) with [Cu(PPh3)3I] or a mixture of CuI and Ph2P(C5H4FeC5H4)PPh2 in aqueous
EtOH/CH2Cl2 leads to mononuclear [Cu(PPh3)2LII] (1), [Cu(PPh3)2LV] (2), [Cu{Ph2P(C5H4FeC5H4)PPh2}LI]
(3), [Cu{Ph2P(C5H4FeC5H4)PPh2}LII] (4), [Cu{Ph2P(C5H4FeC5H4)PPh2}LIII] (5), [Cu{Ph2P(C5H4FeC5H4)PPh2}-
Article history:
Received 30 September 2009
Received in revised form 13 December 2009
Accepted 21 February 2010
Available online 24 February 2010
L
IV] (6) and [Cu{Ph2P(C5H4FeC5H4)PPh2}LV] (7) complexes. The structures of these complexes were inves-
tigated by 1H, 31P{1H} NMR spectroscopy and elemental analysis. The crystal structures of 1, 2 and 4 were
determined by single crystal X-ray diffraction. The complexes 3–7 exhibit emission in the solid state at
ambient temperature that might be explained by the presence of the ferrocene-diyl unit in the chelate
phosphine.
Keywords:
Copper(I)
Crystal structure
Thiourea
Phosphine
Ó 2010 Elsevier B.V. All rights reserved.
NMR spectroscopy
Luminescence
1. Introduction
formed (usually due to missing NH-functions). In contrast to this,
formation of dimers through the thiophosphoryl O atoms goes
In preceding papers, we have described heteroligand Cu(I) com-
plexes with a number of N-thiophosphorylated thioureas and thio-
amides RC(S)NHP(S)(OiPr)2 (R = morpholin-N-yl, piperidin-N-yl
along with the binding of only one PPh3 ligand.
To verify (or falsify) this rule, we have embarked on a system-
atic study on heteroligand Cu(I) complexes, using one HL ligand
and triphenylphosphine (PPh3) or alternatively the chelate phos-
phine Ph2P(C5H4FeC5H4)PPh2 providing a rather large P–Cu–P bite
angle.
On the other hand a number of heteroligand Cu(I) complexes,
containing both aryl-substituted pnictines and cyclic thioureas or
pyridine thiolates, were also described [12–14]. Combination of
these two types of ligands might lead to interesting and unusual
photophysical and electrochemical properties [15].
[1]; a-naphthylNH [2]; NH2 [1,3]; pyridin-2-ylNH, pyridin-3-ylNH,
H2N-6-Py-2-NH [4]; Ph, Et2N [5–7]; (EtO)2P(O)CH2C6H4-4-NH [8];
MeNH, iPrNH, tBuNH, Me2N, PhNH, 2,6-Me2C6H3NH, 2,4,6-
Me3C6H2NH [9,10]), and triphenylphosphine or Ph2P(CH2)nPPh2
(n = 1–3) phosphines. Reaction of alkaline salts of the tetrakis-thio-
urea, containing a cyclam fragment, with [Cu(PPh3)3I] leads to the
tetranuclear Cu(I) complex [{Cu(PPh3)2}4(cyclam)] [11].
Furthermore, we have described two Cu(I) complexes [Cu(PPh3)
{RC(S)NP(S)(OiPr)2}] (R = H2N-6-Py-2-NH [4], (EtO)2P(O)CH2C6H4-
4-NH [8]) (Chart 1), containing one triphenylphosphine ligand.
From this preliminary work it can be supposed, that the coordina-
tion of two molecules of PPh3 to the Cu(I) atom is feasible in cases
where, in the crystal, hydrogen bonded dimers are formed through
the hydrogen atom of the NH group and the sulfur atom of the C@S
fragment, or in cases where no hydrogen bonded dimers can be
2. Results and discussion
The N-thiophosphorylated thioureas HLI–V were prepared as de-
scribed previously [10]. The complexes 1 and 2 were also prepared
according to previously described methods (Scheme 1) [10]. Reac-
tion of the potassium salts of HLI–V with a mixture of CuI and
Ph2P(C5H4FeC5H4)PPh2 in aqueous EtOH/CH2Cl2 leads to the com-
plexes 3–7 (Scheme 2).
* Corresponding authors.
E-mail addresses: damir.safin@ksu.ru (D.A. Safin), axel.klein@uni-koeln.de (A.
Klein).
The complexes 1 and 2 are colorless powders, soluble in ace-
tone, benzene, CH2Cl2, DMSO, DMF and insoluble in n-hexane.
0020-1693/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2010.02.028

1898
D.A. Safin et al. / Inorganica Chimica Acta 363 (2010) 1897–1901
set of signals for the iPrO protons: a singlet, triplet or two doublets
PPh3
H
N
for the CH3 protons at 0.95–1.23 ppm and a doublet of septets or
broad singlet for the CH protons at 4.36–4.65 ppm. In the spectrum
of 3 there are signals for the iPrN protons: a doublet for the CH3
protons at 0.99 ppm and a doublet of septets for the CH protons
at 3.95 ppm. The signal for the tBu and Me protons in the spectra
of 4 and 6, and 7 are found at 1.21 and 2.06–2.22 ppm, respectively.
The signals for the phenyl, aryl and NH protons in the spectra of 3–
7 are at 6.89–7.77 ppm. The 1H NMR spectra contain the signals for
the C5H4 protons at 4.17–4.33 ppm. Signals of the NH group proton
Cu
S
S
P
O
O
H
N
O
O
P
S
H
N
PPh3
N
H
N
S
N
H
Cu
H
N
Cu
H
O
O
H
N
PPh3
S
S
P
O
O
N
P
S
H
N
N
H
N
S
Cu
4
PPh3
in the spectra of 3 and 4 are at 5.62–5.78 ppm. A rather high JP,H
coupling constant (7.5–9.1 Hz) for the NH proton in 3 and 4 is ex-
plained by the so-called W-criterion for the PNCNH chain [16]. The
contribution of the observed splitting to the presence of 4JP,H spin–
spin coupling was unambiguously confirmed by recording 1H NMR
spectra with 31P decoupling.
Crystals of 1, 2 and 4 were obtained by slow evaporation of the
solvent from their dichloromethane–n-hexane mixtures, v/v 1:5
(Table 1). The molecular structures of 1, 2 and 4 are shown in Figs.
1–3, respectively. Selected bond lengths and bond angles are given
in Table 2.
O
O
S
PPh3
O
N
N
CH2 P
P
S
Cu
H
O
O
H
S
P
S
O
P
O
Cu
O
CH2
N
N
O
Ph3P
O
In the structures of 1, 2 and 4 the Cu(I) cation is in a P2S2 tetra-
hedral environment formed by two sulfur atoms of the corre-
sponding deprotonated N-thiophosphoryl thiourea ligand and
two phosphorus atoms of two PPh3 (Figs. 1 and 2) or one
Ph2P(C5H4FeC5H4)PPh2 (Fig. 3). The asymmetric unit of 2 contains
two independent molecules forming a centrosymmetric dimer
through intermolecular hydrogen bonds (Fig. 4). They are formed
by the hydrogen atom of the NH group and the sulfur atom of
the C@S group of a further molecule. The hydrogen bond parame-
ters are following: N(2)–H(2)ꢁ ꢁ ꢁS(2A), N(2)–H(2) 0.83(2) Å,
H(2)ꢁ ꢁ ꢁS(2A) 2.77(2) Å, N(2)ꢁ ꢁ ꢁS(2A) 3.5713(17) Å, \N(2)–H(2)ꢁ ꢁ ꢁ
S(2A) 162.5(18)°; N(2A)–H(2A)ꢁ ꢁ ꢁS(2), N(2A)–H(2A) 0.86(3) Å,
H(2A)ꢁ ꢁ ꢁS(2) 2.56(3) Å, N(2A)ꢁ ꢁ ꢁS(2) 3.3821(18) Å, \N(2A)–
H(2A)ꢁ ꢁ ꢁS(2) 160(2)°. The six-membered CuSPNCS metallocycles
have the conformation of a distorted boat. The fragments NC(S)NP
are almost planar, only the sulfur of the thiophosphoryl group is
significantly deviated from the average planes of these fragments.
This deviation of the phosphoryl sulfur is common for complexes
of N-thiophosphorylated thioureas and thioamides [16].
Chart 1.
H
N
1) KOH
2) [Cu(PPh3)3I]
N
O
O
R
P
S
HLII,V
S
Cu
Ph3P
PPh3
1, 2
R = tBu (1), 2,4,6-Me3C6H2 (2)
Scheme 1.
H
N
N
O
R
P
S
The luminescent properties of 3–7 were investigated in the so-
lid state at room temperature. Previously, we found that the com-
plexes 1 and 2 show no emission under the same conditions [10a].
1) KOH
O
S
2) CuI + Ph2P(C5H4FeC5H4)PPh2
HLI-V
Cu
Ph2P
PPh2
Fe
3-7
R = iPr (3), tBu (4), Ph (5), 2,6-Me2C6H3 (6), 2,4,6-Me3C6H2 (7)
Scheme 2.
The complexes 3–7 are yellow or orange powders, slightly soluble
in acetone, DMSO, DMF, poorly soluble in benzene, CH2Cl2, and
insoluble in n-hexane. 1H, 31P{1H} NMR data indicated that in all
complexes the deprotonated ligands LI–V are 1,5-S,S0-coordinating.
In the 31P{1H} NMR spectra of the complexes, the resonances in
the range 56.2–58.3 ppm correspond to the phosphorus atoms of
the thiophosphoryl group [16]. The signals of Ph2P(C5H4-
FeC5H4)PPh2 in the spectra of the complexes 3–7 exhibit chemical
shifts from ꢀ17.9 to ꢀ17.4 ppm and observed in the area typical
for the coordinated bisphosphines.
The 1H NMR spectra of the complexes 3–7 contain only signals
which correspond to the proposed structures. The spectra contain a
Fig. 1. Thermal ellipsoid representation of the complex 1 (hydrogen atoms were
omitted for clarity). Ellipsoids are drawn at the 30% probability level.

D.A. Safin et al. / Inorganica Chimica Acta 363 (2010) 1897–1901
1899
Table 1
Crystal data, data collection and refinement details for 1, 2 and 4.
1
2
4
Empirical
formula
Formula
weight
Crystal
system
Space group
a (Å)
C47H54CuN2O2P3S2 C52H56CuN2O2P3S2 C45H52CuFeN2O2P3S2
899.49
961.56
929.31
monoclinic
triclinic
triclinic
ꢀ
ꢀ
P21/n
P1
P1
13.0066(8)
21.6122(13)
17.6985(11)
90
111.093(1)
90
11.4710(4)
17.0614(6)
26.1059(9)
74.242(3)
89.937(3)
86.435(3)
4907.0(3)
4
10.9625(9)
12.5534(10)
17.7400(13)
74.108(6)
73.336(6)
78.173(6)
2228.1(3)
2
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
Z
4641.7(5)
4
Dcalc (g cmꢀ3
T (K)
)
1.287
1.302
1.385
293(2)
1888
173(2)
2016
173(2)
968
F(0 0 0)
l
(mm–1
)
0.703
0.669
1.043
Reflections
collected
Unique
38 749
83 997
16 027
Fig. 3. Thermal ellipsoid representation of the complex 4 (hydrogen atoms were
10 826
14 443
4764
omitted for clarity). Ellipsoids are drawn at the 30% probability level.
reflections
Observed
reflections
R indices (all R1 = 0.0320,
data) wR2 = 0.0885
8635 (Rint = 0.024) 18 331
8100 (Rint = 0.0701)
(Rint = 0.0562)
R1 = 0.0428,
wR2 = 0.0743
R1 = 0.0896,
wR2 = 0.0781
The complexes 3 and 4 show a blue emission band at 464–467 nm,
while the complexes 5–7 show cyan emission at 481–487 nm (Ta-
ble 3). Very similar emission maxima were recently reported for
similar mononuclear complexes containing various chelate phos-
phine ligands Ph2P(CH2)nPPh2 (n = 1–3) [10a]. Also, in this study
all complexes containing the monodentate PPh3 ligand failed to
Fig. 4. Hydrogen bonded dimer of 2 (hydrogen atoms except NH were omitted for
clarity).
emit under these conditions, with the exception of the complex
[Cu(PPh3)2(MeNHC(S)NP(S)(OiPr)2)] which shows an emission
band at 429 nm [10a]. The emission around 450–510 nm is typical
of Cu–P containing chromophores with either 3MLCT (d–
r ) or
*
3ILCT (
r–a ) excited states [17]. On the other hand, quite similar
p
emissions have been observed for Zn(II) complexes of N-phosphor-
ylated thioamides and thioureas RC(S)NHP(O)(OiPr)2. Combining
the results from the previous study and the here presented data
we can conclude, that very probably the emission arises from ex-
cited states with a phosphine contribution. The emission of the fer-
rocene-diyl derivatives 3–7 shows a bathochromic shift compared
to the PPh3 derivative with R = MeNH. The failure of the complexes
1 (R = iPrNH) and 2 (R = tBuNH) to show emission compared to the
R = MeNH derivative and the ferrocenyl-diyl derivatives is a strong
argument for the assumption that 3ILCT (
r–a ) excited states are
p
mainly responsible for the emission. While the ferrocene-diyl
derivatives provide sterically favorable (orientation of the Cp group
*
towards the P–Cu bond) and electronically stabilized
p contribu-
tions, most of the PPh3 derivatives fail to do so. For the exceptional
case with R = MeNH the low steric bulk of the Me-substituents al-
lows an optimum orientation of the PPh3 ligand for an efficient sta-
bilization of such a 3ILCT (
r–a ) excited state, while bulkier
p
Fig. 2. Thermal ellipsoid representation of the complex 2 (hydrogen atoms were
omitted for clarity). Ellipsoids are drawn at the 30% probability level.
substituents R = iPr or tBu fail to do so. This is also in line with

1900
D.A. Safin et al. / Inorganica Chimica Acta 363 (2010) 1897–1901
3
Table 2
4H, C5H4), 4.29 (br. s, 4H, C5H4), 4.64 (d. sept, JH,H = 6.1 Hz,
3JP,H = 10.5 Hz, 2H, OCH), 5.62 (t, JHCNH = 4JP,H = 7.5 Hz, 1H, NH),
3
Selected bond lengths (Å) and bond angles (°) for 1, 2 and 4.
1
2a
4
7.24–7.68 (m, overlapped with the solvent signal, Ph) ppm.
31P{1H} NMR: d ꢀ17.6 (br. s, 2P, PPh2), 57.8 (s, 1P, NPS) ppm. Calc.
for C44H50CuFeN2O2P3S2 (915.33): C, 57.74; H, 5.51; N, 3.06. Found:
C, 57.65; H, 5.58; N, 3.02%.
Molecule A
Molecule B
C@S
P@S
P–N
P–O
1.742(2)
1.7388(17)
1.9825(6)
1.6004(14)
1.5827(13),
1.5908(13)
1.315(2)
1.7310(18)
1.9849(6)
1.5881(15)
1.5859(13),
1.5921(13)
1.315(2)
1.741(4)
1.9812(14)
1.613(4)
1.583(3)
1.9752(6)
1.5995(14)
1.5874(12),
1.5896(15)
1.313(2)
4. Yield: 0.376 g (81%). Mp 117–118 °C. 1H NMR: d 1.21 (s, 9H,
CH3, tBu), 1.23 (s, 12H, CH3, iPr), 4.17 (br. s, 4H, C5H4), 4.28 (br. s,
3
3
4H, C5H4), 4.65 (d. sept, JH,H = 6.2 Hz, JP,H = 10.4 Hz, 2H, OCH),
C–N(P)
C–N
Cu–S(C)
Cu–S(P)
Cu–P
1.308(5)
1.355(5)
4
5.78 (d, JP,H = 9.1 Hz, 1H, NH), 7.23–7.70 (m, overlapped with the
1.349(2)
1.356(2)
1.354(2)
solvent signal, Ph) ppm. 31P{1H} NMR: d ꢀ17.5 (br. s, 2P, PPh2),
56.9 (s, 1 P, NPS) ppm. Calc. for C44H52CuFeN2O2P3S2 (929.35): C,
58.16; H, 5.64; N, 3.01. Found: C, 58.24; H, 5.71; N, 2.97%.
5. Yield: 0.408 g (86%). Mp 146–147 °C. 1H NMR: d 1.20 (d,
2.3013(5)
2.3534(5)
2.2991(5),
2.3200(5)
113.47(13)
128.40(13)
118.09(14)
128.99(12)
121.45(6)
107.43(2)
111.01(2)
106.78(2),
109.50(2)
103.14(2),
118.74(2)
109.29(6)
99.78(2)
2.2946(5)
2.3736(5)
2.2775(5),
2.3444(5)
114.20(13)
128.75(13)
117.05(15)
130.24(13)
122.12(6)
107.985(17)
115.763(17)
108.478(19),
120.778(18)
93.498(18),
108.468(18)
109.80(6)
2.2888(5)
2.3545(5)
2.2850(5),
2.3028(5)
2.2919(11)
2.3370(11)
2.2626(12),
2.2937(11)
113.1(3)
128.5(3)
118.5(4)
125.2(3)
120.83(13)
108.06(4)
111.49(4)
109.95(4),
117.05(4)
100.61(4),
108.32(4)
106.62(14)
97.84(5)
S–C–N
115.19(14)
129.22(13)
115.59(16)
134.51(13)
121.48(6)
110.930(17)
113.757(17)
110.498(19),
113.905(19)
98.407(18),
108.656(18)
108.36(6)
3JH,H = 6.1 Hz, 6H, CH3, iPr), 1.23 (d, JH,H = 6.2 Hz, 6H, CH3, iPr),
3
S–C–N(P)
N–C–N
C–N–P
4.24 (br. s, 8H, C5H4), 4.63 (br. s, 2H, OCH), 6.91–7.77 (m, over-
lapped with the solvent signal, Ph + NH) ppm. 31P{1H} NMR: d
ꢀ17.4 (br. s, 2 P, PPh2), 58.3 (s, 1 P, NPS) ppm. Calc. for C47H48Cu-
FeN2O2P3S2 (949.34): C, 59.46; H, 5.10; N, 2.95. Found: C, 59.38; H,
5.14; N, 3.02.
N–P–S
S–Cu–S
P–Cu–P
P–Cu–S(C)
6. Yield: 0.352 g (72%). Mp 132–133 °C. 1H NMR: d 0.95 (t,
3JH,H = 6.2 Hz, 6H, CH3, iPr), 1.04 (t, JH,H = 6.0 Hz, 6H, CH3, iPr),
3
P–Cu–S(P)
2.06 (s, 6H, CH3, Me), 4.18 (br. s, 4H, C5H4), 4.30 (br. s, 4H, C5H4),
Cu–S–C
Cu–S–P
3
3
4.36 (d. sept, JH,H = 6.1 Hz, JP,H = 10.6 Hz, 2H, OCH), 6.89–7.74
(m, overlapped with the solvent signal, Ph + C6H3 + NH) ppm.
31P{1H} NMR: d ꢀ17.9 (br. s, 2 P, PPh2), 56.2 (s, 1 P, NPS) ppm. Calc.
for C49H52CuFeN2O2P3S2 (977.40): C, 60.21; H, 5.36; N, 2.87. Found:
C, 60.32; H, 5.30; N, 2.83.
100.86(2)
100.34(2)
a
Data for two independent molecules A and B.
7. Yield: 0.387 g (78%). Mp 168–169 °C. 1H NMR: d 0.97 (t,
Table 3
Photophysical data for complexes 3–7 (the excitation wavelength was 346 nm).
3JH,H = 6.1 Hz, 6H, CH3, iPr), 1.06 (t, JH,H = 6.2 Hz, 6H, CH3, iPr),
3
Complex Emission maximum (nm) Complex Emission maximum (nm)
2.17 (s, 3H, CH3, Me), 2.22 (s, 6H, CH3, Me), 4.17 (br. s, 4H, C5H4),
3
3
4.33 (br. s, 4H, C5H4), 4.39 (d. sept, JH,H = 6.0 Hz, JP,H = 10.3 Hz,
2H, OCH), 6.70–7.72 (m, overlapped with the solvent signal,
Ph + C6H2 + NH) ppm. 31P{1H} NMR: d ꢀ17.7 (br. s, 2P, PPh2), 56.3
(s, 1P, NPS) ppm. Calc. for C50H54CuFeN2O2P3S2 (991.43): C,
60.57; H, 5.49; N, 2.83. Found: C, 60.69; H, 5.44; N, 2.89.
3
4
5
464
467
481
6
7
485
487
the observation that for the above mentioned derivatives with
Ph2P(CH2)nPPh2 (n = 1–3) ligands emission is observed for most
of the derivatives with the very flexible diphosphine ligand dppp
n = 3, while the dppm (n = 1) and dppe (n = 2) fail to show emis-
sion. We are aware substantiated conclusions cannot be drawn
from the present data. To this end more sophisticated measure-
ments (e.g. at low temperature, in solution, determination of life-
times) are necessary. Such investigations are currently underway.
3.2. Physical measurements
NMR spectra were obtained on a Bruker Avance 300 MHz spec-
trometer at 25 °C. 1H and 31P{1H} NMR spectra in CDCl3 were re-
corded at 299.948 and 121.420 MHz, respectively. Chemical
shifts are reported with reference to SiMe4 (1H) and 85% H3PO4
(
31P{1H}). Fluorescence measurements were carried out on finely
ground solid samples on a Spex FluoroMax-3 spectrofluorometer
at room temperature. Elemental analyses were performed on a
CHNS HEKAtech EuroEA 3000 analyzer.
3. Experimental
N-Thiophosphorylated thioureas HLI–V were prepared according
to previously described methods [10]. The complexes 1 and 2 were
prepared according the previously described methods [10].
3.3. Crystal structure determination and refinement
The X-ray diffraction data for the crystal of 1 were collected on a
Bruker Smart Apex II diffractometer. Data were corrected for
absorption using the SADABS program [18]. The structure was solved
by direct method using the SHELXS97 program [19] and refined by the
full matrix least-squares using SHELXL97 [19]. All non-hydrogen
atoms were refined anisotropically. The hydrogen atoms were lo-
cated on difference map and refined isotropically.
3.1. Synthesis of 3–7
A suspension of HLI–V (0.149, 0.156, 0.166, 0.180 or 0.187 g,
respectively; 0.5 mmol) in aqueous ethanol (35 mL) was mixed
with an ethanol solution of potassium hydroxide (0.031 g,
0.55 mmol).
A
mixture of CuI (0.095 g, 0.5 mmol) and
Ph2P(C5H4FeC5H4)PPh2 (0.277 g, 0.5 mmol) in CH2Cl2 (25 mL) was
refluxed for 0.5 h and then added dropwise under vigorous stirring
to the resulting potassium salt. The mixture was stirred for an hour
and the resulting precipitate of KI was filtered off. The filtrate was
concentrated until crystallization began. Isolated crystals were ob-
tained from a CH2Cl2–n-hexane mixture 5:1 (v/v).
The X-ray diffraction data for the crystals of 2 and 4 were col-
lected on a STOE IPDS-II diffractometer. The images were indexed,
integrated and scaled using the X-Area package [20]. Data were
corrected for absorption using the PLATON program [21]. The struc-
tures were solved by direct methods using the SHELXS program
[19] and all non-hydrogen atoms were refined anisotropically
using SHELXL97 [19]. Hydrogen atoms were revealed from Dq maps
and refined using a riding model. All figures were generated using
the program MERCURY [22].
3. Yield: 0.430 g (94%). Mp 103–104 °C. 1H NMR: d 0.99 (d,
3JH,H = 6.2 Hz, 6H, CH3, iPrN), 1.21 (t, 3JH,H = 6.0 Hz, 12H, CH3, iPrO),
3
3
3.95 (d. sept, JH,H = 6.0 Hz, JHCNH = 7.6 Hz, 1H, NCH), 4.19 (br. s,

D.A. Safin et al. / Inorganica Chimica Acta 363 (2010) 1897–1901
1901
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H. Kozlowski, Z. Anorg. Allg. Chem. 635 (2009) 554.
4. Conclusions
[3] R.C. Luckay, X. Sheng, C.E. Strasser, H.G. Raubenheimer, D.A. Safin, M.G.
Babashkina, A. Klein, Dalton Trans. (2009) 4646.
[4] D.A. Safin, M.G. Babashkina, M. Bolte, F.D. Sokolov, V.V. Brusko, Inorg. Chim.
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[5] N.G. Zabirov, A.Yu. Verat, F.D. Sokolov, M.G. Babashkina, D.B. Krivolapov, V.V.
Brusko, Mendeleev Commun. 13 (2003) 163.
[6] A.Y. Verat, F.D. Sokolov, N.G. Zabirov, M.G. Babashkina, D.B. Krivolapov, V.V.
Brusko, I.A. Litvinov, Inorg. Chim. Acta 359 (2006) 475.
[7] M.G. Babashkina, A.I. Rakhmatullin, D.A. Safin, F. Fayon, F.D. Sokolov, A. Klein,
D.B. Krivolapov, T. Pape, F.E. Hahn, in preparation.
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Krivolapov, I.A. Litvinov, Polyhedron 27 (2008) 2978.
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[10] (a) M.G. Babashkina, D.A. Safin, M. Bolte, A. Klein, CrystEngComm 12 (2010)
134;
Reaction of [Cu(PPh3)3I] or
a
mixture of CuI and
Ph2P(C5H4FeC5H4)PPh2 with the potassium salts of HLI–V has al-
lowed us to obtain mononuclear 1–7 complexes. The complex 2
forms a dimer in the crystal by the NH function and the thiocar-
bonyl S atom of the chelate backbone.
Furthermore, the complexes 3–7 exhibit emission in the solid
state at ambient temperature, which together with previous re-
sults provides some evidence that the emission of such complexes
originates from 3ILCT states and require optimum sterical and elec-
tronical availability of the aromatic substituents on the phospho-
rus atom.
(b) M.G. Babashkina, Ph.D. Thesis, Kazan State University, Kazan, Russian
Federation, 2006.
Acknowledgments
[11] D.A. Safin, M.G. Babashkina, F.D. Sokolov, N.G. Zabirov, J. Galezowska, H.
Kozlowski, Polyhedron 26 (2007) 1113.
[12] A. Kaltzoglou, P.J. Cox, P. Aslanidis, Inorg. Chim. Acta 358 (2005) 3048.
[13] P. Aslanidis, P.J. Cox, S. Divanidis, A.C. Tsipis, Inorg. Chem. 41 (2002) 6875.
[14] T.S. Lobana, R. Sharma, R. Sharma, S. Mehra, A. Castineiras, P. Turner, Inorg.
Chem. 44 (2005) 1914.
This work was supported by the Russian Science Support Foun-
dation. M.G.B. and D.A.S. thank DAAD for the scholarships
(Forschungsstipendien 2008/2009).
[15] V.W.-W. Yam, K.K.-W. Lo, C.-R. Wang, K.-K. Cheung, J. Phys. Chem. A 101
(1997) 4666.
Appendix A. Supplementary material
[16] F.D. Sokolov, V.V. Brusko, N.G. Zabirov, R.A. Cherkasov, Curr. Org. Chem. 10
(2006) 27.
[17] A. Vogler, H. Kunkely, Coord. Chem. Rev. 230 (2002) 243.
[18] G.M. Sheldrick, SADABS, Program for Empirical X-ray Absorption Correction,
Bruker-Nonius, 1990–2004.
[19] G.M. Sheldrick, Acta Crystallogr., Sect. A 64 (2008) 112.
[20] Stoe & Cie, X-AREA. Area-Detector Control and Integration Software, Stoe &
Cie, Darmstadt, Germany, 2001.
[21] A.L. Spek, J. Appl. Crystallogr., Sect. A A36 (2003) 7.
[22] I.J. Bruno, J.C. Cole, P.R. Edgington, M. Kessler, C.F. Macrae, P. McCabe, J.
Pearson, R. Taylor, Acta Crystallogr., Sect. B 58 (2002) 389.
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.ica.2010.02.028.
CCDC 690254, 749403 and 749290 contain the supplementary
crystallographic data 1, 2 and 4. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
References
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