Decomposition of the mixed-ligand silver(I) complex [Ag(PPh 3)2{Et2NC(S)NP(S)(OiPr)2}] with the formation of [Ag(PPh3){Et2NC(S)NP(S)(OiPr)2}], [Ag(PPh3)3NCS

Article abstract of DOI:10.1016/j.inoche.2011.10.005

Reaction of the potassium salt of the N-thiophosphorylated thiourea Et ₂NC(S)NHP(S)(OiPr)₂ (HL) with a mixture of AgNO ₃ and PPh₃ in aqueous EtOH/CH₂Cl₂ leads to the mixed-ligand silver(I)

Full text of DOI:10.1016/j.inoche.2011.10.005

Inorganic Chemistry Communications 15 (2012) 117–120
Contents lists available at SciVerse ScienceDirect
Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Decomposition of the mixed-ligand silver(I) complex
[Ag(PPh3)2{Et2NC(S)NP(S)(OiPr)2}] with the formation of
[Ag(PPh3){Et2NC(S)NP(S)(OiPr)2}], [Ag(PPh3)3NCS]∙(CH3)2 C=O
and Et2NP(S)(OiPr)2
a
b
a
Maria G. Babashkina a, , Damir A. Safin , Michael Bolte , Yann Garcia
⁎
a
Institute of Condensed Matter and Nanosciences, MOST - Inorganic Chemistry, Université Catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve, Belgium
Institut für Anorganische Chemie J.-W.-Goethe-Universität, Frankfurt/Main, Germany
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Reaction of the potassium salt of the N-thiophosphorylated thiourea Et2NC(S)NHP(S)(OiPr)2 (HL) with a
mixture of AgNO3 and PPh3 in aqueous EtOH/CH2Cl2 leads to the mixed-ligand silver(I) complex [Ag
(PPh3)2{Et2NC(S)NP(S)(OiPr)2}] ([Ag(PPh3)2L]). Recrystallization of [Ag(PPh3)2L] from an acetone/n-hexane
mixture leads to the decomposition of the starting complex with the formation of [Ag(PPh3){Et2NC(S)NP(S)
(OiPr)2}] ([Ag(PPh3)L]), [Ag(PPh3)3NCS]∙(CH3)2C=O and Et2NP(S)(OiPr)2. The structures of [Ag(PPh3)2L],
[Ag(PPh3)L], [Ag(PPh3)3NCS]∙(CH3)2C=O and Et2NP(S)(OiPr)2 were all investigated by IR, 31P{1H} and 1H
NMR spectroscopy, and their compositions were established by elemental analysis. The crystal structure of the
complex [Ag(PPh3)3NCS]∙(CH3)2C=O obtained from single crystal X-ray diffraction is presented.
© 2011 Elsevier B.V. All rights reserved.
Received 21 August 2011
Accepted 5 October 2011
Available online 12 October 2011
Keywords:
Coordination chemistry
Crystal structure
Decomposition
N-thiophosphoryl thiourea
Silver(I)
Recently, we have described mixed-ligand Cu(I) complexes with a
number of N-thiophosphorylated thioureas and thioamides RC(S)NHP
(S)(OiPr)2 (NTT) (R=NH2, MeNH, iPrNH, tBuNH, PhNH, 2,6-Me2C6H3NH,
2,4,6-Me3C6H2NH, (EtO)2P(O)CH2C6H4-4-NH, α-naphthyl-NH, pyridin-2-
yl-NH, pyridin-3-yl-NH, H2N-6-Py-2-NH, Me2N, Et2N, morpholin-N-yl,
piperidin-N-yl, Ph) [1–12] or N-thiophosphorylated bis-thioureas Z{NHC
(S)NHP(S)(OiPr)2}2 (Z=o-C6H4, 1,2-CH2CH2) [11,12], and triphenylpho-
sphane or Ph2P(CH2)1–3PPh2 and Ph2P(C5H4FeC5H4)PPh2 phosphanes.
The reaction of alkaline salts of the tetrakis-thiourea, containing a cyclam
fragment, with [Cu(PPh3)3I] leads to the tetranuclear Cu(I) complex [{Cu
(PPh3)2}4(cyclam)] [13]. However, there are only three publications on
mixed-ligand Ag(I) complexes with NTT (R=PhNH, α-naphthyl-NH,
pyridin-3-yl-NH, C5H10N, Ph) [14–16]. It was established that depending
on the synthesis conditions one or two molecules of PPh3 are coordinated
to the metal center. Furthermore, some of the described Ag(I) complexes
show luminescent properties in the solid state [15] and are excellent
precursors for the silver nanoparticles [16].
The N-thiophosphorylated thiourea HL was synthesized as previ-
ously described by the treatment of Et2NH with the isothiocyanate
(iPrO)2P(S)NCS [1,2]. The complex [Ag(PPh3)2L] was prepared by the
following procedure: the ligand was deprotonated in situ using KOH,
followed by reaction with a mixture of AgNO3 and PPh3 (Scheme 1)
[17]. The complex was obtained as a colorless crystalline solid, which
is soluble in most polar solvents.
It is noteworthy that recrystallization of the complex [Ag(PPh3)2L]
from an acetone/n-hexane mixture leads to the decomposition of the
starting complex with the formation of [Ag(PPh3){Et2NC(S)NP(S)
(OiPr)2}] ([Ag(PPh3)L]), [Ag(PPh3)3NCS]∙(CH3)2C=O and Et2NP(S)
(OiPr)2[17]. Nothing similar was observed using other solvents. In all
cases we were able to isolate fine crystalline [Ag(PPh3)2L]. Unfortu-
nately, we were not able to obtain X-ray suitable crystals of [Ag
(PPh3)2L] using other solvents. It should be noted, that no similar reac-
tions were observed for the recently reported mixed-ligand Ag(I) com-
plexes with NTT and phosphanes [14–16], even for the complex with
the piperidine substituent at the thiocarbonyl fragment [16], which is
a close analogue of the complex [Ag(PPh3)2L].
In this contribution, we report on the synthesis and characterization
of the mixed-ligand silver(I) complex [Ag(PPh3)2{Et2NC(S)NP(S)
(OiPr)2}] ([Ag(PPh3)2L]) with Et2NC(S)NHP(S)(OiPr)2 (HL) and triphe-
nylphosphane. The decomposition of the complex [Ag(PPh3)2L] in an
acetone/n-hexane mixture is also studied.
Recently, we have established that the reaction of AgNO3 with the
potassium salt of the N-thiophosphorylated thiourea NH2C(S)NHP(S)
(OiPr)2 gave a new supramolecular silver(I) complex, [Ag(N≡C–NP(S)
(OiPr)2)]n, which contains both tri- and tetracoordinated Ag(I) [18].
The starting ligand had undergone a rearrangement forming the corre-
sponding cyanamido ligand, while the sulfur has been stripped from the
starting thiourea forming H2S and/or K2S. Furthermore, Othman et al.
⁎
Corresponding author.
E-mail address: maria.babashkina@ksu.ru (M.G. Babashkina).
1387-7003/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2011.10.005

118
M.G. Babashkina et al. / Inorganic Chemistry Communications 15 (2012) 117–120
spectra of [Ag(PPh3)2L] and [Ag(PPh3)L] there is a band at 1479
and 1521 cm−1, respectively, corresponding to the conjugated SCN
fragment. In addition, there is a broad intense band arising from
the POC group at 970–984 cm− 1 in the spectra of [Ag(PPh3)2 L],
[Ag(PPh3)L] and Et2NP(S)(OiPr)2. The IR spectrum of the complex
[Ag(PPh3)3NCS]∙(CH3)2C=O contains the characteristic bands for the
C=S and C=N groups at 793 and 1997 cm−1, respectively. These
bands are in the corresponding regions that are characteristic for the
terminal thiocyanate group bonded through the nitrogen atom to the
metal center [21,22]. The acetone molecule in the IR spectrum of the ac-
etone solvate is shown as a band at 1701 cm−1, corresponding to the
C=O group.
Scheme 1. Preparation of the complex [Ag(PPh3)2L].
have described the formation of the complex [Ag(PPh3)3NCS]∙CHCl3 by
the treatment of the dimeric silver(I) complex [Ag2(PPh3)2(CH3COO)2]
with thiosemicarbazide in the ethanol/chloroform mixture [19]. We
suggest, that the acetone molecule provokes the decomposition of [Ag
(PPh3)2L] through the coordination to Ag(I) with the subsequent open-
ing of a six-membered chelate ring, which, in turn, is unstable due to the
influence of the strong electron donor NEt2 group (Scheme 2). This
leads to a rearrangement of the anionic ligand with the elimination of
the NCS group. Thus, the compound Et2NP(S)(OiPr)2 is formed. The tri-
coordinated complex [Ag(PPh3)2NCS] reacts with another molecule of
[Ag(PPh3)2L] with the formation of [Ag(PPh3)L] and [Ag(PPh3)3NCS]
(Scheme 3). Recently, we have reported the similar tricoordinated
Cu(I) complexes [Cu(PPh3)RC(S)NP(S)(OiPr)2] (R=NH2, (EtO)2P(O)
CH2C6H4-4-NH) [4,11,12].
The structures of [Ag(PPh3)2L], [Ag(PPh3)L], [Ag(PPh3)3NCS]∙
(CH3)2C=O and Et2NP(S)(OiPr)2 were investigated by IR, 31P{1H}
and 1H NMR spectroscopy, their compositions were established by el-
emental analysis. The crystal structure of [Ag(PPh3)3NCS]∙
(CH3)2C=O was established from single crystal X-ray diffraction.
The IR spectra of the complexes [Ag(PPh3)2L] and [Ag(PPh3)L]
contain a band at 600 and 596 cm−1, respectively, for the P=S
group of the anionic ligand. These bands are shifted to low frequen-
cies relative to the parent ligand [1,2] as a result of coordination to
the Ag(I) ion. The same band in the IR spectrum of Et2NP(S)(OiPr)2
was observed at 611 cm−1, which is in the region that is characteris-
tic for similar thiophosphorylamides R1R2P(S)(OR3)2 [20]. In the
In the 31P{1H} NMR spectra of the complexes [Ag(PPh3)2L] and
[Ag(PPh3)L] the resonances at 51.1 and 51.4 ppm, respectively, cor-
respond to the phosphorus atom of the thiophosphoryl group. These
signals are shifted high-field relative to that in the spectrum of HL
[1,2]. The signals of the phosphorus atoms of PPh3 in the spectra of
the complexes [Ag(PPh3)2L], [Ag(PPh3)L] and [Ag(PPh3)3NCS]∙
(CH3)2C=O are found at 5.0, 4.7 and 4.8 ppm, respectively. These sig-
nals are markedly low-field shifted compared to that in the spectrum
of the relative Cu(I) complex [Cu(PPh3)2 L] with the same ligand HL
[1,2]. The signal of the phosphorus atom in the 31P{1H} NMR spec-
trum of Et2NP(S)(OiPr)2 was observed at 4.8 ppm, which is in the re-
gion that is characteristic for similar thiophosphorylamides R1R2P(S)
(OR3)2 [20,23].
The 1H NMR spectra of [Ag(PPh3)2L], [Ag(PPh3)L] and Et2NP(S)
(OiPr)2 contain a set of signals for the iPr and Et protons: signals for
the CH3 protons at 1.13–1.34 ppm and signals for the CH2 and CH pro-
tons at 3.58–3.92 and 4.53–4.89 ppm, respectively. Signals of the Et
groups in the spectra of the complexes [Ag(PPh3)2 L] and [Ag(PPh3)
L] are doubled due to hindered rotation, while the methyl protons
of the isopropyl groups are diastereotopic and show two signals.
The signals for the phenyl protons in the spectra of the complexes
[Ag(PPh3)2L], [Ag(PPh3)L] and [Ag(PPh3)3NCS]∙(CH3)2C=O are ob-
served as a multiplet at 7.08–7.50 ppm. The signal for the acetone
Scheme 2. Decomposition of the complex [Ag(PPh3)2L] in the acetone solution.
Scheme 3. Formation of the complexes [Ag(PPh3)L] and [Ag(PPh3)3NCS].

M.G. Babashkina et al. / Inorganic Chemistry Communications 15 (2012) 117–120
119
Table 1
Table 2
Crystal data and data collection details for [Ag(PPh3)3NCS]∙(CH3)2C=O and [Ag
(PPh3)3NCS]∙CHCl3[19].
Selected bond lengths (Å), and bond angles (°) for [Ag(PPh3)3NCS]∙(CH3)2 C=O and
[Ag(PPh3)3NCS]∙CHCl3[19].
[Ag(PPh3)3NCS]∙
(CH3)2C=O
[Ag(PPh3)3NCS]∙CHCl3
[19]
[Ag(PPh3)3NCS]∙(CH3)2 C=O
[Ag(PPh3)3NCS]∙CHCl3
[19]
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
α (°)
β (°)
C58H51AgNOP3S
1020.84
Triclinic
C56H46AgCl3NP3S
1072.13
Triclinic
P 1
13.329(2)
13.647(1)
14.467(1)
89.70(1)
79.47(1)
80.09(1)
2547.7(5)
2
Bond lengths
Ag(1)–N(1)
Ag(1)–P(1)
Ag(1)–P(2)
Ag(1)–P(3)
N(1)–C(1)
C(1)–S(1)
2.3111(16)
2.5825(4)
2.5208(4)
2.5353(4)
1.150(2)
2.319(4)
2.5967(9)
2.5431(9)
2.5561(9)
1.145(5)
1.635(4)
P 1
13.1427(5)
13.6233(5)
14.2212(5)
89.598(2)
79.058(2)
80.483(2)
2464.78(16)
2
1.362
173(2)
0.590
64,157
1.6361(18)
Bond angles
γ (°)
Ag(1)–N(1)–C(1)
N(1)–C(1)–S(1)
N(1)–Ag(1)–P(1)
N(1)–Ag(1)–P(2)
N(1)–Ag(1)–P(3)
P(1)–Ag(1)–P(2)
P(1)–Ag(1)–P(3)
P(2)–Ag(1)–P(3)
160.14(15)
179.8(2)
100.72(4)
105.15(5)
107.44(5)
114.680(14)
112.430(14)
114.821(13)
159.6(3)
178.8(4)
102.58(10)
103.3(6)
107.89(10)
114.73(3)
112.12(3)
114.73(3)
V (Å3)
Z
Dcalc (g cm−3
T (K)
)
1.398
293(2)
0.726
13,101
μ (mm−1
)
Reflections collected
Unique reflections
Observed reflections
8678
8877
17,834 (Rint =0.0178)
11,600 (Rint =0.0165)
Final R indices [I>2σ(I)] R1 =0.0334, wR2 =0.0892 R1 =0.0513, wR2 =0.1641
Torsion angles
P(1)–Ag(1)–N(1)–C(1)
P(2)–Ag(1)–N(1)–C(1)
P(3)–Ag(1)–N(1)–C(1)
−38.8(5)
80.6(5)
−156.6(5)
29.0(11)
−90.6(10)
147.5(10)
CH3 protons is observed at 2.10 ppm in the 1H NMR spectrum of [Ag
(PPh3)3NCS]∙(CH3)2C=O.
In summary, the reaction of the potassium salt of the N-
thiophosphorylated thiourea Et2NC(S)NHP(S)(OiPr)2 (HL) with a
mixture of AgNO3 and PPh3 in aqueous EtOH/CH2Cl2 leads to the
mixed-ligand silver(I) complex [Ag(PPh3)2L]. The recrystallization
of the complex [Ag(PPh3)2L] from an acetone/n-hexane mixture
leads to the decomposition of the starting complex with the forma-
tion of [Ag(PPh3)L], [Ag(PPh3)3NCS]∙(CH3)2C=O and Et2NP(S)
(OiPr)2. According to the X-ray data, the silver(I) cation is in a NP3
tetrahedral environment formed by three phosphorus atoms of the
PPh3 ligands and the nitrogen atom of the NCS ligand in the complex
[Ag(PPh3)3NCS]∙(CH3)2C=O. Acetone molecules are trapped in the
crystal.
The crystal structure of the solvate [Ag(PPh3)3NCS]∙(CH3)2C=O was
determined by a single crystal X-ray diffraction analysis (Table 1) [24].
The molecular structure of the acetone solvate complex in the crystal
is shown in Fig. 1. Selected bond lengths and bond angles are given in
Table 2. The crystal structure of another solvate (with chloroform)
was earlier described [19]. The cell parameters, bond lengths, and
bond and torsion angles of ref. [19] are similar to our structure (Tables 1
and 2), the differences observed being due to the lower temperature
(173 K) of our measurement compared to the previous report (293 K).
The crystal structure of [Ag(PPh3)3NCS]∙(CH3)2C=O was solved and
refined in the triclinic space group P 1. In the structure of the acetone
solvate, the Ag(I) cation is in a NP3 tetrahedral environment formed
by three phosphorus atoms of the triphenylphosphane ligands and
the nitrogen atom of the isothiocyanate ligand (Fig. 1). The angles
about the silver atom deviate significantly from 100.72(4)° to 114.821
(13)°. The N(1)–C(1)–S(1) angle is 179.8(2)° indicating the linearity
of this fragment. The Ag(1)–N(1)–C(1) angle is 160.14(15)° and fits
well in the range characteristic for the majority of the M–NCS com-
plexes [19].
Acknowledgments
This work was partly funded by the Fonds National de la
Recherche Scientifique-FNRS (FRFC No. 2.4508.08, IISN 4.4507.10)
and the IAP INANOMAT program. We thank the F.R.S.-FNRS (Belgium)
for a post-doctoral position allocated to D. A. S.
Appendix A. Supplementary material
CCDC 805545 contains the supplementary crystallographic
data for [Ag(PPh3)3NCS]∙(CH3)2C=O. 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. Supplementary materials related to this article can be
found online at doi:10.1016/j.inoche.2011.10.005.
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M.G. Babashkina et al. / Inorganic Chemistry Communications 15 (2012) 117–120
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3
3
1521 (SCN). 1H NMR δ (ppm): 1.13 (t, JH,H =6.8 Hz, 3H, CH3, Et), 1.27 (t, JH,H
=
6.9 Hz, 3H, CH3, Et), 1.23 (d, 3JH,H=6.0 Hz, 6H, CH3, iPr), 1.34 (d, 3JH,H=6.1 Hz, 6H,
3
3
CH3, iPr), 3.64 (q, JH,H=6.9 Hz, 2H, CH2, Et), 3.93 (q, JH,H=6.9 Hz, 2H, CH2, Et),
3 3
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393 (1972) 309.
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[23] B. Kaboudin, M. Karimi, H. Zahedi, Organic Preparations and Procedures Interna-
tional 40 (2008) 399.
[24] The X-ray diffraction data for the crystal of [Ag(PPh3)3NCS]∙(CH3)2C=O were
collected on a STOE IPDS-II diffractometer. The images were indexed, integrated
and scaled using the X-Area package [25]. Data were corrected for absorption
using the PLATON program [26]. The structures were solved by direct methods
using the SHELXS program [27] and refined first isotropically and then anisotropical-
ly using SHELXL97 [27]. Hydrogen atoms were revealed from Δρ maps and refined
using a riding model. The figure was generated using the program Mercury [28].
[25] Stoe & Cie, X-Area. Area-Detector Control and Integration Software, Stoe & Cie,
Darmstadt, Germany, 2001.
[26] A.L. Spek, Journal of Applied Crystallography 36 (2003) 7.
[27] G.M. Sheldrick, Acta Crystallographica A64 (2008) 112.
[28] I.J. Bruno, J.C. Cole, P.R. Edgington, M. Kessler, C.F. Macrae, P. McCabe, J. Pearson, R.
Taylor, Acta Crystallographica. Section B, Structural Science 58 (2002) 389.
Chemical shifts are reported with reference to SiMe4 (1H) and 85% H3PO4
(
31P
{1H}). Elemental analyses were performed on a Thermoquest Flash EA 1112 Ana-
lyzer from CE Instruments. Synthesis of[Ag(PPh3)2L]: A suspension of HL (0.156 g,
0.5 mmol) in aqueous ethanol (10 mL) was mixed with an aqueous ethanol solu-
tion (10 mL) of potassium hydroxide (0.031 g, 0.55 mmol). A mixture of AgNO3
(0.085 g, 0.5 mmol) and PPh3 (0.262 g, 1 mmol) in CH2Cl2 (20 mL) was refluxed
for 0.5 h and then added dropwise under vigorous stirring to the resulting potas-
sium salt. The mixture was stirred for an hour and the resulting precipitate of KI
was filtered off and the solvent was then removed in vacuum. The residue was
recrystallized from a CH2Cl2/n-hexane mixture (1:5, v/v). Isolated yield 0.406 g
(86%). IR ν (cm−1): 600 (P=S), 970 (POC), 1479 (SCN). 1H NMR δ (ppm): 1.16
3
3
3
(t, JH,H=6.9 Hz, 3H, CH3, Et), 1.23 (t, JH,H=7.0 Hz, 3H, CH3, Et), 1.28 (d, JH,H
=
3
3
6.2 Hz, 6H, CH3, iPr), 1.32 (d, JH,H=6.2 Hz, 6H, CH3, iPr), 3.58 (q, JH,H =7.0 Hz,
3
3
2H, CH2, Et), 3.89 (q, JH,H =6.9 Hz, 2H, CH2, Et), 4.74 (d. sept, JPOCH =10.8
Hz, JH,H =6.1 Hz, 2H, OCH), 7.29–7.46 (m, 30H, Ph, PPh3); 31P{1H} NMR δ
3
(ppm): 5.0 (2P, PPh3), 52.1 (1P, NPS); Anal. Calc. for C47H54AgN2O2P3S2
(943.87): C 59.81, H 5.77, N 2.97. Found: C 59.70, H 5.71, N 3.02%. Synthesis
ofEt2NP(S)(OiPr)2,[Ag(PPh3)3NCS]∙(CH3)2C=O,[Ag(PPh3)L]: Recrystallization
of the complex [Ag(PPh3)2L] from an acetone/n-hexane mixture (1:3, v/v)
after three days leads to the formation of the colorless crystals of [Ag(PPh3)3-
NCS]∙(CH3)2C=O, which were isolated by decantation. Isolated yield 0.211 g
(97%). IR ν (cm−1): 793 (C=S), 1701 (C=O), 1997 (C=N). 1H NMR δ (ppm):