On the Reactivity of Thiourea Derivatives with Silver(I) Oxide

Article abstract of DOI:10.1002/ejic.202000308

Aryl thioureas of the type ArNHC(S)NR₂ react with Ag₂O to form the corresponding silver(I) thioureato complexes. Depending on the nature of the thiourea, either insoluble materials, zig-zag coordination polymers or discrete tetranuclear silver species were isolated and structurally characterised. These thioureato complexes react with one, two or three equivalents of a phosphine ligand, forming a series of compounds with various structural motifs and different coordination numbers at the metal. The spectroscopic properties and structures of several of these compounds are discussed.

Full text of DOI:10.1002/ejic.202000308

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Silver Thioureato Complexes
On the Reactivity of Thiourea Derivatives with Silver(I) Oxide
Sarah K. Pilz[a] and Fabian Mohr*[a]
Abstract: Aryl thioureas of the type ArNHC(S)NR2 react with thioureato complexes react with one, two or three equivalents
Ag2O to form the corresponding silver(I) thioureato complexes. of a phosphine ligand, forming a series of compounds with
Depending on the nature of the thiourea, either insoluble mate- various structural motifs and different coordination numbers at
rials, zig-zag coordination polymers or discrete tetranuclear sil- the metal. The spectroscopic properties and structures of
ver species were isolated and structurally characterised. These several of these compounds are discussed.
Introduction
thioureas of the type ArC(O)NHC(S)NR2, resulting in the forma-
tion of hexanuclear silver(I) complexes containing O,S-chelating
acylthioureato-ligands.[8] In continuation of this work, we report
here results of our studies of the reactivity of several aryl thio-
ureas of the type ArNHC(S)NR2 with silver(I) oxide.
Silver, in marked contrast to its heavier neighbour below, can
adopt coordination numbers two, three, four and six, resulting
in an enormous structural diversity. The soft Ag+-ion naturally
prefers soft bases, in particular sulfur-containing ligands. From
a more practical point of view, silver compounds have been
used in the treatment of 2nd and 3rd degree burns since the
1960's and silver sulfadiazine is considered an essential medi-
cine by the WHO.[1] Recent work has focused on both antitu-
mor- and antibacterial-activity of silver compounds.[2] Indeed,
silver has been in medical use since ancient times,[3] however its
antibacterial activity was only discovered in the late nineteenth
century.[4] This antibacterial activity of metallic silver and silver
nanoparticles is currently experiencing a renaissance, especially
in the battle against multi-drug-resistant pathogens.[5] Some
fundamental silver coordination chemistry goes back to the
days of silver-based photography and thermal imaging, both
applications being based on the light- and thermal-sensitivity
of many silver compounds.[6] Since the majority of simple silver
salts are poorly soluble, the range of suitable precursors, which
are soluble in common laboratory solvents, is rather limited.
Thus, most silver coordination compounds are typically pre-
pared from AgNO3 or AgOAc. In 1998, Lin developed the use of
silver(I) oxide as both base and source of silver-ions in the syn-
thesis of N-heterocyclic carbene complexes of silver from imid-
azolium salts.[7] The method is so robust, versatile and general,
that is has become known as the “silver oxide route”. More
recently, we showed that Ag2O can readily deprotonate acyl-
Results and Discussion
We initially selected the 4-nitro-substituted thioureas 4-
O2NC6H4NHC(S)NR2 (R = Me 1, Allyl 2) in our investigation, since
past experience has taught us that complexes containing 4-
nitro-substituted derivatives as ligands crystallise well. To see if
the nitro-group has any electronic- or steric effect, we also used
the phenyl-counterparts PhNHC(S)NR2 (R = Me 3, Ally 4). Thus,
the 4-nitro-substituted thioureas 4-O2NC6H4NHC(S)NR2 (R = Me
1, Allyl 2) react at room temperature with Ag2O in a mixture of
MeOH and CH2Cl2 forming a solution, out of which yellow crys-
tals (1a, 2a, Scheme 1) can be isolated. The phenyl-counterparts
of (1) and (2) PhNHC(S)NR2 (R = Me 3, Ally 4) also react with
Ag2O, however, in this case, the products are poorly soluble in
common solvents and precipitate out during the reaction. Since
we were thus unable to obtain any NMR spectroscopic data
or single crystals of these products, we used them directly in
subsequent reactions (see below).
[a] S. K. Pilz, Prof. Dr. F. Mohr
Anorganische Chemie, Fakultät für Mathematik und Naturwissenschaften,
Bergische Universität Wuppertal,
42119 Wuppertal, Germany
E-mail: fmohr@uni-wuppertal.de
Scheme 1. Reactions of the 4-nitro substituted thioureas with silver(I) oxide.
ORCID(s) from the author(s) for this article is/are available on the WWW
under https://doi.org/10.1002/ejic.202000308.
The asymmetric unit of the NMe2-derivative 1a (Figure 1)
contains one molecule of the deprotonated thiourea bound to
two different silver atoms through the sulfur atom. The two
sulfur–silver bond lengths of 2.3810(11) and 2.3881(10) Å are
very similar, thus the deprotonated thiourea can be described
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as a symmetric μ2-thiolato ligand. Between the two silver atoms
there is an argentophilic Ag···Ag contact of 3.2101(4) Å.[9] Fur-
thermore, the aryl ring of thiourea unit is oriented in such a
way, that the two of the carbon atoms from the arene ring bind
to one silver atom in a η2-manner with carbon–silver distances
of about 2.97 and 3.13 Å. Such η2-bonding of an arene ring to
a silver atom is not uncommon; however, the C-Ag distances
typically are somewhat shorter, ranging from about 2.4 to
2.7 Å.[10]
Figure 3. The polymer chain of [Ag{4-O2NC6H4NC(S)NMe2}]∞ (1a) showing
only the silver and sulfur atoms.
Such a zig-zag silver coordination polymer is unique and has
so far, to the best of our knowledge, never been observed.
Structurally related thiosemicarbazones RC=NN(H)C(S)NH2 form
discrete hexanuclear Ag-clusters of the type [Ag6(L)6] (L = de-
protonated thiosemicarbazone), several examples of which
have been structurally characterized.[11] In one case, a tetranu-
clear complex [Ag4(L)4] (L = deprotonated thiosemicarbazone)
has also been reported.[12] Similarly, we previously obtained
hexanuclear silver clusters from the reaction of acylthioureas
ArC(O)NHC(S)NR2 with Ag2O.[8] Others have isolated tetranu-
clear species of the type [Ag4(L)4] (L = deprotonated acylthio-
urea) when AgNO3 was used as silver precursor.[13] Both tetra-
and hexanuclear silver compounds have also been reported
with deprotonated thiocarbohydrazone ligands of the type RC=
NNHC(S)NHNH2.[14]
Figure 1. The asymmetric unit of [Ag{4-O2NC6H4NC(S)NMe2}]∞ 1a. Ellipsoids
are drawn at the 30 % level. Hydrogen atoms have been omitted for clarity.
The coordination polymer is formed by the asymmetric units
arranged in a head-to-tail manner, resulting in linear S-Ag–S
units, which are arranged in a zig-zag pattern (Figure 2 and
Figure 3). Both silver centres are four-coordinate (bound to two
different sulfur- and two different silver-atoms), however, one
silver atom has two additional η2-bound arene rings at the
“axial” positions, resulting in an almost octahedral coordination
environment.
The asymmetric unit of the allyl complex 2a (Figure 4) con-
sists of a square of four silver atoms which are symmetrically
Figure 2. The coordination polymer [Ag{4-O2NC6H4NC(S)NMe2}]∞ (1a) show-
ing the two different silver sites. Hydrogen atoms as well as the NO2-groups
have been omitted for clarity.
Figure 4. The asymmetric unit of [Ag{4-O2NC6H4NC(S)NAllyl2}]4 2a. Ellipsoids
are drawn at the 30 % level. Hydrogen atoms have been omitted for clarity
and only one part of the disordered allyl-groups is shown.
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bridged by a sulfur atom of the deprotonated thiourea. The between two carbon atoms and a silver atom of around 2.9 Å
thioureas are arranged around the Ag4-square in an alternating are formed. Based on these crystal structures, we can therefore
pattern above and below the plane, respectively (Figure 5). Each formulate 1a as the coordination polymer [Ag{4-
silver is four-coordinate, being bound to two other silver atoms O2NC6H4NC(S)NMe2}]∞ and 2a as the tetranuclear cluster [Ag{4-
and two sulfur atoms. The nitrogen atoms of the thiourea are O2NC6H4NC(S)NAllyl2}]4.
not involved in the coordination to silver.
Addition of either one or two equivalents (per silver) of a
phosphine [Ph3P or 1,3,5-triaza-7-phosphaadamantane (PTA)] to
a solution or suspension formed upon stirring the thioureas
with Ag2O, yellow-orange or colourless crystalline compounds
were isolated in reasonable yields (Scheme 2). These two phos-
phines are sterically quite different (PTA is sterically similar to
Me3P), thus allowing us to observe how this might affect molec-
ular structures of the complexes. In all cases examined here, the
thioureato ligand remains bound to the silver and is not dis-
placed by the phosphine.
31P-NMR spectra of the complexes confirm coordination of
the phosphines to a silver centre. Furthermore, from their pro-
ton NMR spectra the 1:1 or 2:1 ratio of phosphine and the re-
Figure 5. The Ag4S4 core of [Ag{4-O2NC6H4NC(S)NAllyl2}]4 2a showing only
the silver-, sulfur- and carbon-atoms bound to sulfur.
The four Ag–Ag bond lengths range from 3.088(2) Å to
3.2432(4) Å, and are similar to those observed in other tetranu-
clear silver complexes containing bridging thiolato ligands in-
cluding [Ag{SSi(OtBu)3}]4 (Ag–Ag = 3.15 and 3.11 Å),[15] [Ag{4-
O2NC6H4C(O)NC(S)NEt2}]4 (Ag–Ag
=
2.99 and 3.05 Å),[8]
[Ag{PhC(O)NC(S)NEt2}]4 (Ag–Ag = 3.02 and 3.12 Å)[13a] and
[Ag{PhC(O)NC(S)NnBu2}]4 (Ag–Ag = 2.97 and 3.02 Å).[13b] The S-
Ag bond lengths (ca. 1.8 Å) are all very similar and typical for
symmetric μ2-thiolates. Although allyl-groups can coordinate to
silver in a η2-fashion with bond lengths of around 2.4 Å,[16] here
the distances between the ally groups and the silver atoms are
greater than 3 Å, too far for any significant interaction. The aryl
rings of the thiourea are however oriented such that a η2-bonds
Figure 6. Molecular structure of [Ag(PPh3){4-O2NC6H4NC(S)NMe2}]2 1b. Ellip-
soids are drawn at the 30 % level. Hydrogen atoms have been omitted for
clarity.
Scheme 2. Reactions of the thioureas with silver(I) oxide and different ratios of phosphines.
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Figure 7. Molecular structure of [Ag(PTA){4-O2NC6H4NC(S)NMe2}]2 1c. Ellip-
soids are drawn at the 30 % level. Hydrogen atoms have been omitted for
clarity.
Figure 9. Molecular structure of [Ag(PTA){4-O2NC6H4NC(S)NAllyl2}]2 2c. Ellip-
soids are drawn at the 50 % level. Hydrogen atoms have been omitted for
clarity.
Figure 8. Molecular structure of [Ag(PPh3){PhNC(S)NMe2}]2 3b. Ellipsoids are
drawn at the 30 % level. Hydrogen atoms have been omitted for clarity.
spective deprotonated thiourea is evident. The solid-state struc-
tures of several examples were determined by X-ray diffraction.
The structures can be categorised into two groups: dinuclear
complexes with bridging thioureato ligands (Figure 6, Figure 7,
Figure 8, and Figure 9) and mononuclear species with S-bound
thioureato ligands (Figure 10, Figure 11, and Figure 12).
In all four cases, dinuclear complexes are formed, containing
an Ag2S2-paralelogram. Here too the deprotonated thiourea
acts as a symmetric μ2-thiolato ligand. The silver atom is tricoor-
dinate, bound to two sulfur atoms and a phosphorus atom from
the phosphine. In addition, there is also an interaction between
two carbon atoms of the arene ring with the silver ranging from
Figure 10. Molecular structure of [Ag(PPh3)2{4-O2NC6H4NC(S)NAllyl2}] 2b.
Ellipsoids are drawn at the 50 % level. Hydrogen atoms have been omitted
for clarity. Only the ipso-carbon atoms of the Ph3P ligands are shown.
ca. 2.7 Å to 3.1 Å; slightly longer than what is typically found.[10] each other with Ag···Ag distances of about 3.05 Å and 3.16 Å,
In two of the compounds the silver atoms are quite close to indicative of an argentophilic attraction.[9]
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Figure 11. Molecular structure of [Ag(PPh3)2{PhNC(S)NAllyl2}] 4b. Ellipsoids are
drawn at the 50 % level. Hydrogen atoms have been omitted for clarity. Only
the ipso-carbon atoms of the Ph3P ligands are shown.
Figure 12. Molecular structure of [Ag(PPh3)3{Ph(Me)NC(S)N(Allyl)}] (5a).
Hydrogen atoms have been omitted for clarity and only one part of the
disordered ally group is shown. Only the ipso-carbon atoms of the Ph3P li-
gands are shown.
The bis(phosphine) complexes 2b (Figure 10) and 4b (Fig-
ure 11) are discrete mononuclear silver(I) complexes with a tet-
rahedral environment. Two phosphines as well as the S-bound
deprotonated thiourea coordinate to the silver. In addition, the
aryl-ring is η2-bound to the silver atom, with C-Ag distances
ranging from 2.97 to 3.24 Å.
With the structurally related thiourea Ph(Me)NC(S)NH(Allyl)
(5) we were unable to isolate a soluble product from its reaction
with Ag2O. However, the insoluble, probably polymeric material,
reacted with excess Ph3P to give a colourless compound, which
from proton NMR spectroscopy contained Ph3P and the depro-
tonated thiourea in a ratio of 3:1 as well as a significant amount
of Ph3PO (Scheme 3).
cated about 0.7 Å above the centre of this base and the sulfur
atom of the thioureato-ligand forms the tip of the slightly dis-
torted pyramid. The Ag-S vector is tilted by about 17° from a
line perpendicular to the base. A similar structural arrangement
is found in a number of other tris(triphenylphosphine)silver(I)
complexes containing anionic sulfur ligands including
[Ag(PPh3)3(2-mercaptopyridine)] and [Ag(PPh3)3(thiosaccharin-
ate)].[17]
Despite several purification attempts and repeated prepara-
tions, we could not isolate the material in a spectroscopically
pure form. From one reaction we obtained a few X-ray quality
crystals, which allowed us to determine the molecular structure.
The molecule consists of a silver atom, bound to three Ph3P
ligands and to the sulfur atom of the deprotonated thiourea
(Figure 12).
The reaction of thiourea 5 with AgNO3 in MeCN without ad-
dition of a base affords a colourless, crystalline solid (Scheme 3).
The proton NMR spectrum of this material clearly shows the
presence of the NH-proton, confirming that the thiourea is not
deprotonated. A single crystal structure analysis revealed that
the compound is an AgNO3 complexes containing the neutral
thiourea (Figure 13). The asymmetric unit thus consists of a sil-
The four-coordinate geometry of the silver atom may be de- ver atom bound to the nitrate ion via oxygen and the sulfur
scribed as trigonal pyramidal. The three phosphorus atoms atom of the neutral thiourea. The coordination sphere about
form the almost equilateral (P–P distances of 4.25, 4.32 and the silver is completed by the allyl-group η2-bound to the
4.26 Å) triangular base of the pyramid. The silver atom is lo- metal.
Scheme 3. Reactions of thiourea 5 with different silver compounds.
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react with one, two or three equivalents of a phosphine, gener-
ating a variety of structurally diverse phosphine complexes.
These include monomeric trigonal pyramidal species, dinuclear
S-bridged complexes as well as tricoordinated compounds. In
each case there may also be additional π-bonding between the
aryl rings and the silver or the allyl-group and silver. Both the
nature of the aryl-substituents (4-nitro-group vs. proton) and
the alkyl-groups (Me or Allyl) influence the structures of the
compounds that are formed. The silver(I) complexes containing
the 4-nitro-derivates are more soluble when compared to those
of their phenyl-counterparts. Similarly, the NMe2-derivative
forms a polymeric structure, whereas the more sterically de-
manding allyl-substituted ligand seems to favour the tetranu-
clear cluster.
Figure 13. Molecular structure of [Ag(NO3){Ph(Me)NC(S)NH(Allyl)}]∞ 5b. Ellip-
soids are drawn at the 30 % level and hydrogen atoms have been omitted
for clarity.
Experimental Section
General: Reagents and solvents (HPLC grade) were obtained from
commercial suppliers and were used as received. Reactions were
carried out under ambient conditions shielded from light, without
exclusion of air or moisture. The thioureas 1,[19] 2,[20] 3[21] and 4[20]
as well as PTA[22] were prepared as previously reported. NMR spec-
tra were recorded on a Bruker Avance 400 or a Bruker Avance III
600 spectrometer. Chemical shifts are referenced externally against
This unit assembles into a zig-zag-shaped 1D-coordination
polymer (Figure 14), in which the sulfur atom of the thiourea
bridges two silver centres. Overall, the silver atom is four-coordi-
nate.
Me4Si (1H and 13C) or 85 % H3PO4 31P). Elemental analyses were
(
carried out by staff of the in-house microanalytical facility using an
Elementar Vario EL instrument.
[Ag{4-O2NC6H4NC(S)NMe2}]∞ (1a): To
a
solution of 4-
O2NC6H4NHC(S)NMe2 (0.105 g, 0.466 mmol) in a 1:1 mixture of
MeOH and CH2Cl2 (20 mL) was added Ag2O (0.064 g, 0.276 mmol).
After ca. 15 min. almost all Ag2O had dissolved and the mixture
was filtered through Celite. The filtrate deposited yellow needles
suitable for X-ray diffraction after standing undisturbed for two
days. A total of 0.030 g (23 %) yellow crystals could be isolated.
These crystals were used for X-ray diffraction and NMR spectro-
scopic analysis. 1H NMR (CDCl3): δ = 3.37 (s, 6 H, NMe2), 7.37 (d, J =
8.7 Hz, 2 H, C6H4), 8.19 (d, J = 8.6 Hz, 2 H, C6H4). 13C NMR (CDCl3):
δ = 41.69 (NMe2), 122.35 (C6H4), 124.76 (C6H4), 143.54 (CNO2),
147.33 (ipso-C6H4), 179.95 (CS). Elemental analyses calcd. for
C9H10N3O2SAg (287.1): C 32.55, H 3.03, N 12.65; found C 32.39, H
3.13, N 12.72 %.
Figure 14. Molecular structure of [Ag(NO3){Ph(Me)NC(S)NH(Allyl)}]∞ 5b show-
ing the zig-zag coordination polymer. Ellipsoids are drawn at the 30 % level.
Only parts of the thiourea and nitrate ligands are shown. Hydrogen atoms
have been omitted for clarity.
[Ag{4-O2NC6H4NC(S)NAllyl2}]4 (2a): To
O2NC6H4NHC(S)NAllyl2 (0.100 g, 0.361 mmol) in CH2Cl2 (20 mL) was
added Ag2O (0.0585 g, 0.252 mmol). Workup as described above
a
solution of 4-
The two C-Ag bond lengths in complex 5b are 2.491(2) Å and
2.501(2) Å, respectively. In related Ag(I) coordination polymers
containing 1,3-diallylurea and its derivatives, the corresponding
bond lengths are slightly shorter (ca. 2.3 Å).[18] The silver–sulfur
bond lengths of the symmetric bridging thiourea ligands are
2.46 Å and 2.53 Å, consistent with a symmetrical thiolato-
bridge.
1
afforded a total of 0.0898 g (65 %) yellow crystals. H NMR (CDCl3):
δ = 4.19 (d, J = 5.1 Hz, 8 H, NCH2), 5.19 (d, J = 17.1 Hz, 4 H, CH2),
5.24 (d, J = 10.1 Hz, 4 H, CH2), 5.88 (ddt, J = 15.4, 10.1, 5.1 Hz, 4 H,
CH), 6.53 (d, J = 8.3 Hz, 8 H, C6H4), 8.15 (d, J = 8.3 Hz, 8 H, C6H4).
The compound was not soluble enough to obtain a meaningful
13C NMR spectrum. Elemental analyses calcd. for C52H56N12O8S4Ag4
(1536.8): C 40.64, H 3.67, N 10.94; found C 40.59, H 3.51, N 10.80 %.
Conclusion
[Ag(PPh3){4-O2NC6H4NC(S)NMe2}]2 (1b): To
a solution of 4-
O2NC6H4NHC(S)NMe2 (0.121 g, 0.537 mmol) in a 1:1 mixture of
MeOH and CH2Cl2 (20 mL) was added Ag2O (0.063 g, 0.272 mmol).
After ca. 15 min. the mixture was filtered through Celite. To the
filtrate solid Ph3P (0.140 g, 0.534 mmol) was added and the solution
was carefully layered with hexanes. By the next day yellow-orange
plates had deposited, which were isolated by filtration, washed with
hexanes and dried in air. A total of 0.159 g (51 %) yellow-orange
We have shown that silver(I) oxide can act as both base and
source of silver ions in reactions with arylthioureas. Depending
on the nature of the thioureas, poorly soluble polymeric com-
pounds are obtained or soluble complexes are formed when
the aryl ring bears a nitro-group. These soluble compounds
crystallise as either a polymeric zig-zag chain or as a discrete
tetranuclear silver complex. These thioureato silver complexes crystals were obtained. 1H NMR (CDCl3): δ = 3.20 (s, 6 H, NMe2),
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6.78 (d, J = 9.0 Hz, 2 H, C6H4), 7.20–7.28 (m, 6 H, o-Ph3P), 7.36–7.43
(m, 6 H, m-Ph3P), 7.44–7.50 (m, 3 H, p-Ph3P), 7.84 (d, J = 9.0 Hz, 2
H, C6H4). 13C NMR (CDCl3): δ = 40.47 (NMe2), 121.97 (C6H4), 125.42
0.104 mmol) and PTA (0.055 g, 0.0.350 mmol). A total of 0.0322 g
(69 %) colourless crystals were obtained. H NMR (CDCl3): δ = 3.25
(s, 6 H, NMe2), 4.10 (d, J = 4.6 Hz, 6 H, PTA), 4.54 (AB quart., J =
1
(C6H4), 129.09 (d, J = 10.1 Hz, m-Ph3P), 130.78 (d, J = 1.9 Hz, p-Ph3P), 13.9 Hz, 6 H, PTA), 6.72 (dd, J = 8.3, 1.2 Hz, 2 H, o-Ph), 6.94 (tt, J =
130.86 (d, J = 31.4 Hz, ipso-Ph3P), 133.64 (d, J = 16.2 Hz, o-Ph3P),
140.84 (CNO2), 157.31 (ipso-C6H4), 168.49 (CS). 31P{1H} NMR (CDCl3):
δ = 11.37 (s). Elemental analyses calcd. for C54H50N6P2S2Ag2
(1188.8): C 54.56, H 4.24, N 7.07; found C 54.59, H 4.34, N 7.12 %.
7.4, 1.2 Hz, 1 H, p-Ph), 7.32–7.37 (m, 2 H, m-Ph). 13C NMR (CDCl3):
δ = 40.36 (Me), 51.15 (d, J = 1.5 Hz, PTA), 73.35 (d, J = 5.5 Hz, PTA),
121.08 (p-Ph), 121.78 (o-Ph), 129.95 (m-Ph), 152.65(ispo-Ph), 164.46
(CS). 31P{1H} NMR (CDCl3): δ = –89.2 (s).
[Ag(PPh3)2{PhNC(S)NAllyl2}] (4b): This was prepared as described
above using PhNHC(S)NAllyl2 (0.161 g, 0.691 mmol), Ag2O (0.111 g,
0.478 mmol) and Ph3P (0.362 g, 1.38 mmol). A total of 0.3997 g
(67 %) pale yellow crystals were obtained. 1H NMR (CDCl3): δ = 4.42
(dt, J = 5.6, 1.4 Hz, 4 H, NCH2), 5.13 (dq, J = 10.1, 1.4 Hz, 2 H, CH2),
5.20 (dq, J = 17.2, 1.4 Hz, 2 H, CH2), 5.99 (ddt, J = 17.2, 10.1, 5.6 Hz,
2 H, CH), 6.27 (t, J = 7.3 Hz, 1 H, p-Ph), 6.73 (d, J = 7.6 Hz, 2 H, o-
Ph), 6.89 (7, J = 7.6 Hz, 2 H, m-Ph), 7.26–7.37 (m, 24 H, m-Ph3P, o-
Ph3P), 7.38–7.43 (m, 6 H, p-Ph3P). 13C NMR (CDCl3): δ = 51.28 (NCH2),
115.43 (CH2), 120.16 (p-Ph), 121.64 (o-Ph), 128.66 (d, J = 9.0 Hz, m-
Ph3P), 129.80 (d, J = 1.4 Hz, p-Ph3P), 129.85 (m-Ph), 133.33 (d, J =
16.5 Hz, ipso-Ph3P), 133.87 (d, J = 17.2 Hz, o-Ph3P), 135.61 (CH). Due
to limited solubility, signals for the ipso-Ph and CS carbon atoms
were not observed. 31P{1H} NMR (CDCl3): δ = 5.79 (s). Elemental
analyses calcd. for C49H45N2P2SAg (863.8): C 68.13, H 5.25, N 3.24;
found C 68.05, H 4.99, N 3.45 %.
[Ag(PTA){4-O2NC6H4NC(S)NMe2}]2 (1c): This was prepared as de-
scribed above using 4-O2NC6H4NHC(S)NMe2 (0.095 g, 0.422 mmol),
Ag2O (0.049 g, 0.211 mmol) and PTA (0.066 g, 0.420). A total of
1
0.162 g (79 %) yellow crystals were obtained. H NMR (CDCl3): δ =
3.26 (s, 6 H, NMe2), 4.08 (d, J = 4.4 Hz, 4 H, PCH2N), 4.53 (AB system,
J = 13.6 Hz, 6 H, NCH2N), 6.74 (d, J = 9.1 Hz, 2 H, C6H4), 8.19 (d, J =
9.1 Hz, 2 H, C6H4). 13C NMR (CDCl3): δ = 40.26 (NMe2), 51.10 (d, J =
3.8 Hz, PCH2N), 73.29 (d, J = 6.1 Hz, NCH2N), 121.92 (C6H4), 125.88
(C6H4), 140.28 (CNO2), 160.09 (ipso-C6H4), 165.48 (CS). 31P{1H} NMR
(CDCl3):
δ
=
–88.82 (s). Elemental analyses calcd. for
C30H44N12O4P2S2Ag2 (978.6): C 36.82, H 4.53, N 17.18; found C 37.09,
H 4.47, N 17.37 %.
[Ag(PPh3)2{4-O2NC6H4NC(S)NAllyl2}] (2b): This was prepared as
described above using 4-O2NC6H4NHC(S)NAllyl2 (0.2099 g,
0.757 mmol), Ag2O (0.1234 g, 0.533 mmol) and Ph3P (0.3990 g,
1.520 mmol). A total of 0.5297 g (89 %) orange crystals were ob-
tained. 1H NMR (CDCl3): δ = 4.42 (d, J = 5.6 Hz, 4 H, NCH2), 5.41 (dq,
J = 10.1, 1.4 Hz, 2 H, CH2), 5.20 (dq, J = 17.2, 1.6 Hz, 2 H, CH2), 5.94
(ddt, J = 17.2, 10.1, 5.6 Hz, 2 H, CH), 6.69 (d, J = 9.0 Hz, 2 H, C6H4),
7.19–7.26 (m, 12 H, o-Ph3P), 7.30–7.36 (m, 12 H, m-Ph3P), 7.39–7.45
(m, 6 H, p-Ph3P), 7.58 (d, J = 9.0 Hz, 2 H, C6H4). 13C NMR (CDCl3):
δ = 51.57 (NCH2), 115.95 (CH2), 122.15 (C6H4), 125.31 (C6H4), 128.84
(d, J = 9.1 Hz, m-Ph3P), 130.08 (d, J = 1.5 Hz, p-Ph3P), 132.69 (d, J =
19.8 Hz, ipso-Ph3P), 133.65 (d, J = 16.8 Hz, o-Ph3P), 134.89 (CH),
139.32 (C6H4), 160.70 (C6H4), 167.69 (CS). 31P{1H} NMR (CDCl3): δ =
6.44 (s).
[Ag(PTA){PhNC(S)NAllyl2}]2 (4c): This was prepared as described
above using PhNHC(S)NAllyl2 (0.162 g, 0.697 mmol), Ag2O (0.114 g,
0.492 mmol) and PTA (0.109 g, 0.696 mmol). A total of 0.194 g
1
(56 %) colourless crystals were obtained. H NMR (CDCl3): δ = 4.10
(d, J = 4.9 Hz, 6 H, PTA), 4.31 (dt, J = 5.7, 1.6 Hz, 4 H, NCH2), 4.56 (s,
6 H, PTA), 5.14–5.23 (m, 4 H, CH2), 5.95 (ddt, J = 17.2, 10.1, 5.6 Hz,
2 H, CH), 6.66 (d, J = 7.6 Hz, 2 H, o-Ph), 6.92 (tt, J = 7.3, 1.3 Hz, 1 H,
p-Ph), 7.31–7.38 (m, 2 H, m-Ph). 13C NMR (CDCl3): δ = 51.11 (PTA),
51.46 (NCH2), 73.41 (d, J = 5.5 Hz, PTA), 115.89 (CH2), 121.45 (o-Ph),
130.31 (m-Ph), 134.99 (CH). Due to poor solubility signals for the
ipso-Ph and CS carbon atoms were not observed. 31P{1H} NMR
[Ag(PTA){4-O2NC6H4NC(S)NAllyl2}]2 (2c): This was prepared as de-
scribed above using 4-O2NC6H4NHC(S)NAllyl2 (0.210 g, 0.757 mmol),
Ag2O (0.123 g, 0.533 mmol) and PTA (0.399 g, 1.520 mmol). A total
of 0.530 g (89 %) orange crystals were obtained. 1H NMR (CDCl3):
δ = 4.07 (d, J = 4.3 Hz, 6 H, PTA), 4.30 (dt, J = 5.7, 1.5 Hz, 4 H, NCH2),
4.53(AB quart., J = 13.8 Hz, 6 H, PTA), 5.16–5.19 (m, 2 H, CH2), 5.20–
5.23 (m, 2 H, CH2), 5.91 (ddt, J = 17.5, 9.8, 5.6 Hz, 2 H, CH), 6.72 (d,
J = 9.0 Hz, 2 H, C6H4), 8.19 (d, J = 9.0 Hz, 2 H, C6H4). 13C NMR
(CDCl3): δ = 51.08 (d, J = 4.3 Hz, PTA), 51.79 (NCH2), 73.25 (d, J =
6.1 Hz, PTA), 116.45 (CH2), 121.90 (C6H4), 125.66 (C6H4), 134.16 (CH),
140.31 (C6H4), 160.18 (C6H4), 163.64 (CS). 31P{1H} NMR (CDCl3): δ =
–88.73 (s).
(CDCl3):
δ
=
–90.22 (s). Elemental analyses calcd. for
C38H54N10P2S2Ag2 (992.8): C 45.97, H 5.48, N 14.11; found C 45.91,
H 5.38, N 14.01 %.
PhN(Me)C(S)NH(Allyl) (5): A preparation of this compound is men-
tioned in the literature without any details.[23] We provide here a
description of our synthesis method of this compound together
with NMR spectroscopic data. To a solution of N-methylaniline
(5 mL, 0.05 mmol) in Et2O (15 mL) containing Et3N (1 drop) allyl
isothiocyanate (5 mL, 0.05 mmol) was added dropwise at room tem-
perature. After removal of the solvent, 10.2 g (98 %) of an orange oil
was obtained. This crude material was used directly in subsequent
reactions. 1H NMR (CDCl3): δ = 3.56 (s, 3 H, Me), 4.22 (tt, J = 5.5,
1.6 Hz, 2 H, NCH2), 4.98 (d, J = 1.5 Hz, 1 H, CH2), 5.02 (ddt, J = 7.3,
2.9, 1.5 Hz, 1 H, CH2), 5.38 (br. s, 1 H, NH), 5.72–5.82 (m, 1 H, CH),
7.22 (dd, J = 8.4, 1.3 Hz, 2 H, o-Ph), 7.38 (t, J = 7.5 Hz, 1 H, p-Ph),
7.47 (t, J = 7.5 Hz, 2 H, m-Ph). 13C NMR (CDCl3): δ = 43.23 (Me),
47.94 (NCH2), 115.85 (CH2), 126.86 (o-Ph), 128.41 (p-Ph), 130.14 (m-
Ph), 133.82 (CH), 142.57 (ipso-Ph), 181.86 (CS).
[Ag(PPh3){PhNC(S)NMe2}]2 (3b): This was prepared as described
above using PhNHC(S)NMe2 (0.045 g, 0.250 mmol), Ag2O (0.029 g,
0.125 mmol) and Ph3P (0.065 g, 0.248 mmol). A total of 0.091 g
1
(66 %) colourless crystals were obtained. H NMR (CDCl3): δ = 3.21
(s, 6 H, NMe2), 6.48 (t, J = 7.3 Hz, 1 H, p-Ph), 6.67 (d, J = 7.9 Hz, 2
H, o-Ph), 7.01 (t, J = 7.5 Hz, 2 H, m-Ph), 7.29–7.34 (m, 6 H, o-Ph3P),
7.37–7.41 (m, 6 H, m-Ph3P), 7.43–7.48 (m, 3 H, p-Ph3P). 13C NMR
(CDCl3): δ = 40.05 (NMe2), 120.89 (p-Ph), 121.40 (o-Ph), 128.85 (d,
J = 9.8 Hz, m-Ph3P), 130.17 (m-Ph), 130.40 (d, J = 1.8 Hz, p-Ph3P),
131.69 (d, J = 27.8 Hz, ipso-Ph3P), 133.96 (d, J = 16.5 Hz, o-Ph3P),
154.30 (ipso-Ph), CS not observed. 31P{1H} NMR (CDCl3): δ = 11.20
(s). Elemental analyses calcd. for C54H52N4P2S2Ag2 (1098.8): C 59.03,
H 4.77, N 5.10; found C 59.09, H 4.74, N 5.07 %.
[Ag(PPh3)3{PhN(Me)C(S)N(Allyl)}] (5a): A suspension containing 5
(0.1033 g, 0.501 mmol) and Ag2O (0.080 g, 0.345 mmol) in CH2Cl2
(20 mL) was stirred at room temperature overnight. The mixture
was passed through Celite and Ph3P (0.3943 g, 1.503 mmol) was
added. Removal of the solvent gave a beige solid. Based on 31P
NMR data this material contained about 4 % Ph3PO. Despite re-
peated attempts with various purification methods and reaction
conditions, we were unable to obtain the complex in spectroscopi-
cally pure form. 1H NMR (CDCl3): δ = 3.70 (s, 3 H, Me), 4.22–4.27 (m,
[Ag(PTA){PhNC(S)NMe2}]2 (3c): This was prepared as described
above using PhNHC(S)NMe2 (0.0312 g, 0.173 mmol), Ag2O (0.0242 g,
Eur. J. Inorg. Chem. 2020, 1–11
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7
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
doi.org/10.1002/ejic.202000308
EurJIC
European Journal of Inorganic Chemistry
Table 1. Crystallographic and refinement details for complexes 1a, 2a, 1b, 3c, 2c, and 3b are reported herein.
1a
2a
1b
3c
2c
3b
CCDC code
1992683
C9H10N3O2SAg
332.13
Monoclinic
C2/c
1992687
1992689
1992688
1992682
1992690
Empirical formula
C52H56N12O8S4Ag4 C54H50N6P2S2Ag2 C30H44N12O4P2S2Ag2 C38H52N12O4P2S2Ag2 C54H52N4P2S2Ag2
Formula weight
1536.80
Monoclinic
P21/c
1188.80
Monoclinic
P21/c
978.57
Monoclinic
P21/n
1082.71
Monoclinic
P21/n
1098.79
Triclinic
Crystal system
Space group
P1
¯
a/Å
10.9747(8)
21.9840(13)
10.1327(9)
90
13.8000(7)
20.3483(8)
20.8870(10)
90
15.8104(4)
12.5978(3)
13.9945(3)
90
9.3650(2)
11.8472(3)
16.9486(3)
90
9.0684(4)
13.0850(8)
18.3265(8)
90
9.9406(4)
10.0423(4)
13.0953(5)
76.980(4)
78.284(4)
73.427(4)
1207.19(9)
1
b/Å
c/Å
α/°
ꢀ/°
115.201(9)
90
92.045(4)
90
109.332(3)
90
94.431(2)
90
96.683(4)
90
γ/°
Volume/Å3
2212.0(3)
8
5861.5(5)
4
2630.21(12)
2
1874.81(7)
2
2159.85(19)
2
Z
ρ
calc mg/mm3
1.995
1.741
1.501
1.733
1.665
1.511
μ/mm–1
1.998
1.522
0.936
1.295
1.133
1.005
F(000)
1312.0
3072.0
1208.0
992.0
1104.0
560.0
Crystal size/mm3
2Θ range
0.02 × 0.04 × 0.12 0.03 × 0.06 × 0.12 0.07 × 0.07 × 0.12 0.04 × 0.06 × 0.13
4.948 to 58.908 ° 4.978 to 58.998 ° 4.674 to 58.884 ° 4.818 to 58.758 °
0.04 × 0.05 × 0.05
4.806 to 58.48 °
11363
0.05 × 0.06 × 0.11
4.896 to 58.822 °
11247
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
5865
32947
15817
9862
2597
13748
6155
4307
4953
5550
2597/0/149
1.075
13748/0/757
1.026
6155/0/318
1.042
4307/0/237
1.052
4953/2/271
1.032
5550/0/291
1.038
R1 = 0.0552,
wR2 = 0.1467
R1 = 0.0370,
wR2 = 0.0660
R1 = 0.0304,
wR2 = 0.0645
R1 = 0.0276, wR2
0.0572
=
R1 = 0.0274, wR2
0.0514
=
R1 = 0.0281,
wR2 = 0.0547
Final R indices [I > 2σ(I)]
Largest difference peak/hole/ 3.44/–1.65
e Å3
1.26/–0.66
0.48/–0.45
0.41/–0.39
0.37/–0.34
0.46/–0.38
2 H, NCH2), 5.01–5.09 (m, 2 H, CH2), 5.83 (ddt, J = 17.1, 10.7, 5.5 Hz,
1 H, CH), 7.23–7.29 (m, Ph, Ph3P, Ph3PO), 7.32–7.40 (m, Ph, Ph3P,
Ph3PO). 31P{1H} NMR (CDCl3): δ = 3.33 (s, 5a), 28.87 (s, Ph3PO). A few
X-ray quality crystals formed upon slow evaporation of the reaction
mixture during one of the preparations.
and empirical absorption correction was carried out using the Crys-
Alis Pro program package.[24] The structure was solved using Direct
Methods and refined by Full-Matrix-Least-Squares against F2 using
SHELXT and SHELXL.[25] Non-hydrogen atoms were refined aniso-
tropically and hydrogen atoms were placed at idealized positions
and refined using the riding model. All calculations were carried
out using the Olex2 graphical interface.[26] Important crystallo-
graphic and refinement details are collected in Table 1 and Table 2.
[Ag(NO3){PhN(Me)C(S)NH(Allyl)}]∞ (5b): To
a solution of 5
(0.124 g, 0.600 mmol) in CH2Cl2 (10 mL) was added solid AgNO3
(0.104 g, 0.612 mmol). The solution deposited colourless crystals on
standing for a few days. The solid was isolated by filtration and was
washed with water and Et2O. After drying a total of 0.112 g (50 %)
CCDC 1992683 (for 1a), 1992687 (for 2a), 1992689 (for 1b), 1992688
(for 3c), 1992682 (for 2c), 1992690 (for 3b), 1992684 (for 2b),
1992685 (for 4b), 1992686 (for 5a), and 1992681 (for 5b) contain
the supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre.
1
colourless crystals were obtained. H NMR ([D6]DMSO): δ = 3.50 (s,
3 H, Me), 4.16 (t, J = 5.2 Hz, 2 H, NCH2), 5.13–5.22 (m, 2 H, CH2),
5.91 (ddt, J = 17.2, 9.7, 4.8 Hz, 1 H, CH), 7.30 (dd, J = 8.5, 1.2 Hz, 2
H, o-Ph), 7.41 (t, J = 7.4 Hz, 1 H, p-Ph), 7.50 (t, J = 7.8 Hz, 2 H, m-
Ph), 8.25 (t, J = 5.8 Hz, 1 H, NH). 13C NMR ([D6]DMSO): δ = 42.83
(Me), 47.96 (NCH2), 114.36 (CH2), 126.91 (o-Ph), 128.12 (p-Ph), 130.06
(m-Ph), 133.94 (CH), 144.22 (ipso-Ph), 177.96 (CS). Elemental analy-
ses calcd. for C11H14N3O3S3Ag (376.2): C 35.12, H 3.75, N 11.17;
found C 36.40, H 3.72, N 11.01 %.
Keywords: Silver · Thiourea ligands · P ligands ·
Coordination modes · Structure elucidation
X-ray Crystallography: Data were collected at 150 K using a Rigaku
Oxford Diffraction Gemini E Ultra diffractometer, equipped with an
EOS CCD area detector and a four-circle kappa goniometer. For the
data collection, the Mo source emitting graphite-monochromated
Mo-Kα radiation (λ = 0.71073 Å) was used. Data integration, scaling
[1] World Health Organization model list of essential medicines, World Health
Organisation, 2019.
[2] a) S. Medici, M. Peana, V. M. Nurchi, M. A. Zoroddu, J. Med. Chem. 2019,
62, 5923–5943; b) H. A. Mohamed, C. E. Willans, J. Organomet. Chem.
Eur. J. Inorg. Chem. 2020, 1–11
www.eurjic.org
8
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
doi.org/10.1002/ejic.202000308
EurJIC
European Journal of Inorganic Chemistry
Table 2. Crystallographic and refinement details for complexes 2b, 4b, 5a, and 5b reported herein.
2b
4b
5a
5b
CCDC code
1992684
C49H44N3O2P2SAg
908.74
1992685
C49H45N2P2SAg
863.74
1992686
C65H58N2P3SAg
1099.97
Triclinic
1992681
C11H14N3O3SAg
376.18
Empirical formula
Formula weight
Crystal system
Triclinic
Triclinic
Monoclinic
P21/c
Space group
P1
¯
P1
¯
P1
¯
a/Å
12.3505(4)
13.7210(6)
14.4215(5)
73.588(3)
83.548(3)
64.554(4)
2116.77(15)
2
12.0974(4)
13.7559(5)
14.4750(5)
73.289(3)
83.189(3)
64.750(3)
2086.62(14)
2
11.1617(3)
11.8360(4)
21.7466(8)
82.915(3)
83.028(2)
74.166(3)
2731.22(16)
2
9.9190(7)
7.1143(6)
20.8801(13)
90.0
b/Å
c/Å
α/°
ꢀ/°
98.344(7)
90.0
γ/°
Volume/Å3
1457.83(18)
4
Z
ρ
calc mg/mm3
1.426
1.375
1.338
1.714
μ/mm–1
0.645
0.646
0.538
1.532
F(000)
936.0
892.0
1140.0
752.0
Crystal size/mm3
2Θ range
0.08 × 0.10 × 0.13
4.668 to 58.944 °
19329
0.05 × 0.05 × 0.10
4.754 to 58.938 °
20702
0.03 × 0.12 × 0.13
4.972 to 58.894 °
27296
0.05 × 0.05 × 0.10
5.294 to 58.66 °
7398
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
9810
9615
12584
3384
9810/0/523
1.053
9615/0/496
1.033
12584/24/668
1.042
3384/0/173
1.033
R1 = 0.0287, wR2 = 0.0616 R1 = 0.0322, wR2
=
R1 = 0.0330, wR2
0.0676
=
R1 = 0.0299, wR2 = 0.0602
Final R indices [I > 2σ(I)]
0.0732
Largest difference peak/hole/e Å3
0.72/–0.35
1.77/–0.41
0.46/–0.35
0.74/–0.79
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Received: March 30, 2020
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Silver Thioureato Complexes
S. K. Pilz, F. Mohr* .......................... 1–11
On the Reactivity of Thiourea Deriv-
atives with Silver(I) Oxide
Aryl thioureas ArNHC(S)NR2 react with These thioureato complexes react with
Ag2O to form silver(I) thioureato com- phosphines, forming a series of prod-
plexes, which are either insoluble ma- ucts with a variety of structures and
terials, zig-zag coordination polymers, coordination numbers at the silver
or discrete tetranuclear silver clusters. centre.
doi.org/10.1002/ejic.202000308
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