One cationic dinuclear silver(I) complex of dppatc formed in situ by replacing ethylenediamine units of dppeda through aminothiocarbamide

Article abstract of DOI:10.1016/j.inoche.2011.07.002

Reaction of silver nitrate with N,N,N′,N′- tetra(diphenylphosphanylmethyl)ethylenediamine (dppeda) in the presence of aminothiocarbamide in CH₂Cl₂/MeOH afforded an unexpected and low-yield binuclear complex [Ag₂(dppatc)₂](NO ₃)₂?2MeOH (dppatc = N,N-bis(diphenylphosphanylmethyl) aminothiocarbamide) (1). An X-ray analysis revealed that the [Ag ₂(dppatc)₂]²⁺ dication of 1 contains a centrosymmetric double half-open cage structure in which two Ag centers are bridged by a pair of the heteroscopionate dppatc ligands via four Ag-μ-S and four AgP bonds. The in situ-formed dppatc ligand in 1 could be readily generated by one-pot and high-yield reaction of diphenylphosphine with formaldehyde and aminothiocarbamide. Further reaction of AgNO₃ with dppatc could produce 1 in a relatively high yield. The results provided an efficient route to the synthesis of dppatc and also an interesting insight into its coordination chemistry.

Full text of DOI:10.1016/j.inoche.2011.07.002

Inorganic Chemistry Communications 14 (2011) 1665–1668
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Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
One cationic dinuclear silver(I) complex of dppatc formed in situ by replacing
ethylenediamine units of dppeda through aminothiocarbamide
Duan-Xiu Li a, Zhi-Gang Ren a, Hui-Fang Wang a, Jian-Ping Lang a,b,
⁎
a
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, Jiangsu,
People's Republic of China
b
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, People's Republic of China
a r t i c l e i n f o
a b s t r a c t
Article history:
Reaction of silver nitrate with N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylenediamine (dppeda) in the
presence of aminothiocarbamide in CH2Cl2/MeOH afforded an unexpected and low-yield binuclear complex
[Ag2(dppatc)2](NO3)2·2MeOH (dppatc=N,N-bis(diphenylphosphanylmethyl)aminothiocarbamide) (1). An
X-ray analysis revealed that the [Ag2(dppatc)2]2+ dication of 1 contains a centrosymmetric double half-open
cage structure in which two Ag centers are bridged by a pair of the heteroscopionate dppatc ligands via four
Ag-μ-S and four Ag\P bonds. The in situ-formed dppatc ligand in 1 could be readily generated by one-pot and
high-yield reaction of diphenylphosphine with formaldehyde and aminothiocarbamide. Further reaction of
AgNO3 with dppatc could produce 1 in a relatively high yield. The results provided an efficient route to the
synthesis of dppatc and also an interesting insight into its coordination chemistry.
Received 25 May 2011
Accepted 5 July 2011
Available online 13 July 2011
Keywords:
Silver(I)
N,N-bis(diphenylphosphanylmethyl)
aminothiocarbamide
Crystal structure
Aminothiocarbamide
In situ formation
© 2011 Elsevier B.V. All rights reserved.
In the past decades, synthesis of polynuclear silver(I) coordination
compounds of P,S-mixed ligands received much attention due to their
rich structural chemistry and their potential applications in advanced
materials including sulfide-based glasses and solid electrolytes [1,2].
Among them, many compounds have separate phosphine and thiolate
ligands coordinate at silver(I) centers [3]. Only few examples have been
reported to hold the P and S donor atoms in the same ligand [4]. On the
other hand, the chemistry of coordination compounds with multipho-
sphine ligands has been extensively investigated because of their
interesting structures and their abundant applications in catalysis,
medicine and optical materials [5–7]. For instance, reaction of AgNO3
and AgCl with one tetraphosphine ligand, N,N,N′,N′-tetra(diphenylpho-
sphanylmethyl)ethylene diamine (dppeda), gave rise to a cationic
binuclear basket-shaped complex [Ag2(dppeda)Cl](NO3) [8]. It is noted
that the presence of chloride was critical in the formation of this
complex. Then two questions come out. Is it possible to introduce a
sulfide or a sulfur-containing species in such a system? What other
structures could be anticipated? Within these questions in mind, we
selected aminothiocarbamide, which could be a sulfide reagent, to
introduce into reactions of AgNO3 with dppeda. Unexpectedly, another
cationic binuclear complex containing an in situ-formed ligand N,N-bis
(diphenylphosphanylmethyl)aminothiocarbamide (dppatc), [Ag2
(dppatc)2](NO3)2 (1) was isolated in a low yield. The ligand dppatc
contains one S and two P donor atoms and its coordination chem-
istry has never been reported before. In this communication we report
the rational synthesis and structural characterization of dppatc and
complex 1.
Sulfide urea is known to give an inorganic sulfide through the
cleaving its C_S bond by heating or binding to metals [9]. Therefore we
expected that aminothiocarbamide may work in a similar way to create
sulfides for aggregating Ag+ ions. Treatment of AgNO3 with equimolar
dppeda in the presence of equimolar aminothiocarbamide in CH2Cl2/
MeOH led to the formation of 1 in 9% yield [10] (Scheme 1). According to
its X-ray structure described later, no inorganic sulfide was generated
from the cleavage of the C_S bond of aminothiocarbamide. On the
contrary, aminothiocarbamide replaced the ethylenediamine unit of
dppeda to form two equiv of dppatc. In this process, the four C\N bonds
of dppeda were cleaved to four Ph2PCH2+ species while two C\N bonds
for each dppatc were generated by aminothiocarbamide to link two
Ph2PCH2+ species. The C\N cleavage and regeneration and the
coordination of S and P atoms to silver(I) centers may be completed
in situ in a cooperative way. Intriguingly, direct reactions of dppeda with
one or two equiv. of aminothiocarbamide without Ag+ failed to produce
this ligand. After numerous attempts, we found that one-pot reaction of
aminothiocarbamide with 2 equiv. of diphenylphosphine and excess
formaldehyde could readily produce dppatc in 97% yield (Scheme 2)
[11]. With pure and large scale of dppatc in hands, reactions of dppatc
with silver(I) salts were quite straightforward. Treatment of dppatc with
equimolar AgNO3 in CH2Cl2/MeOH gave rise to 1 in 72% yield [10]. Thus
we supposed that the presence of Ag+ was quite critical in the formation
of dppatc during the reactions of dppeda with aminothiocarbamide. The
⁎
Corresponding author at: Key Laboratory of Organic Synthesis of Jiangsu Province,
College of Chemistry, Chemical Engineering and Materials Science, Soochow University,
Suzhou 215123, Jiangsu, People's Republic of China. Tel./fax: +86 512 65882865.
E-mail address: jplang@suda.edu.cn (J.-P. Lang).
1387-7003/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2011.07.002

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D.-X. Li et al. / Inorganic Chemistry Communications 14 (2011) 1665–1668
Scheme 1. Synthesis of the title complex 1.
Ag+ ion was assumed to induce the in situ replacement of ethylenedia-
mine unit of dppeda via aminothiocarbamide and facilitate the
formation of dppatc via its binding to the P and S atoms.
groups of two different dppatc ligands and two S atoms from C_S of
two different dppatc ligands, forming a distorted tetrahedral
geometry. The mean Ag\P bond length (2.4378(9) Å) in 1 is close to
that of [Ag2(dppm)2(L)2] (2.432(3) Å, dppm=bis(diphenylphosphino)
methane, L=N,N′-diethyldithiocarbamate) [16], but slightly shorter
than that of [Ag(PPh3)2 L] (2.474(2) Å, L=pyrazolecarbodithiolate)
[15]. The average Ag\S bond length (2.7069(11) Å) is longer than
those of [Ag(PPh3)2 L] (2.670(2) Å, L=pyrazolecarbodithiolate) and
[Ag2(dppm)2(L)2] (2.662(3) Å, L=N,N′-diethyldithiocarbamate). The
Ag(1)···Ag(1A) contact of 3.3956(11) Å is slightly shorter than the sum
of the van der Waals radii of two Ag atoms (3.44 Å), and may suggest they
are related by so-called agentophilicity [17].
The photoluminescent properties of dppatc and 1 in the solid state at
room temperature were investigated. Upon excitation at 243 nm,
dppatc exhibited photoluminescence with emission maxima at
390 nm (Fig. S3). However 1 exhibited no photoluminescence which
may be ascribed to the fact that binding of Ag+ to dppatc caused its
fluorescence to be quenched. The thermogravimetric analyses revealed
that 1 was stable in room temperature (Fig. S4). The first weight loss of
4.79% in the region of 20 °C −160 °C roughly corresponds to the weight
loss of all the methanol molecules (calculated 4.65%). The second loss of
77.57% (160 °C–800 °C) is ascribed to the loss of nitrate and the dppatc
ligands (calculated 77.70%). The decomposition residual species was
assumed to be silver oxide.
In summary, we demonstrated that reaction of AgNO3 with dppeda
and aminothiocarbamide produced one unique Ag/dppatc complex 1.
Compound 1 holds a cationic double half-open cage structure in which
two Ag centers are linked by a pair of the heteroscopionate dppatc
ligands through four Ag-μ-S and four Ag\P bonds. The in situ-formed
dppatc ligand could be readily generated by one-pot and high-yield
reaction of diphenylphosphine with formaldehyde and aminothiocar-
bamide. We are currently extending this work by studies on the
assembly of other novel dppatc-based arrays from its reactions of other
metals such as Cu(I), Au(I) and Pd(II).
The ligand dppatc is soluble in CHCl3, CH2Cl2, DMF, and DMSO, and
insoluble in MeOH, MeCN and Et2O. Compound 1 is soluble in DMSO, and
insoluble in common solvents. The elemental analyses were consistent
with their formulas. In the IR spectrum of 1, the strong bands at 1483,
1435, 843, 741, and 694 cm−1 were assigned to the phosphino groups of
dppatc. The 1H NMR spectrum of dppatc showed signals related to protons
of the methylene groups, the amido groups and the phenyl groups at
3.69–3.89, 5.57–5.90 and 7.26–7.33 ppm, respectively. A single broad
doublet resonance at 8.40 ppm was observed for the phosphino groups of
dppatc in the 31P{1H} NMR of 1(Fig. S1). The chemical shift from 8.40 ppm
(1) to dppatc (−26.4 ppm) may be due to the coupling between the 31
P
and 107Ag(108Ag) nuclei [8,12]. In order to gain more insight into the
stability of 1 in solution, we measured its positive electrospray ionization
mass spectrum (ESI-MS) in DMSO. It exhibited a set of peaks assignable to
[Ag2(dppatc)2]2+ (m/z=596.0) and [Ag2(dppatc-H)2]+ (m/z=1189.1)
(Fig. S2). The existence of these two cationic fragments suggested that
the dication of 1 was quite stable in solution, which also confirmed
why dppatc was preferably formed from the reaction of dppeda with
aminothiocarbamide in the presence of Ag+ ion.
Compound 1·2MeOH crystallizes in the triclinic space group Pī and
the asymmetric unit consists of half a [Ag2(dppatc)2]2+ dication, one
NO3− anion and one MeOH solvent molecule [13]. The structure of the
dication of 1 was presented in Fig. 1. Each dppatc ligand shows a
scorpion-like structure, which may resemble the so-called mono-
anionic “scorpionate” ligand [15]. Each of its two P atoms binds one
Ag+ and one S bridges two Ag centers to form an half-open
[Ag2S2P2C2N2] cage. Two cages share the [Ag2S2] rhomb to form a
double half-open cage with a crystallographic center of symmetry
located at the middle of Ag(1)···Ag(1A) contact. Such a structure is
uncommon in the metal complexes of monoanionic “scorpionate”
ligand. Each Ag(I) atom in 1 is coordinated by two P atoms from the PPh2
Scheme 2. Synthesis of the ligand dppatc.

D.-X. Li et al. / Inorganic Chemistry Communications 14 (2011) 1665–1668
1667
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This work was financially supported by the National Natural Science
Foundation of China (20871088, 20901054, and 90922018), the Nature
Science Key Basic Research of Jiangsu Province for Higher Education
(09KJA150002), the Specialized Research Fund for the Doctoral Program
of higher Education of Ministry of Education (20093201110017), the
State Key Laboratory of Coordination Chemistry of Nanjing University,
the Qin-Lan and the “333” Projects of Jiangsu Province, and the
“Soochow Scholar” Program and the Program for Innovative Research
Team of Suzhou University. We also thanked the helpful suggestions
from the reviewers and the editor.
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[10] Synthesis of 1: Method 1: To a suspension of AgNO3 (17 mg, 0.1 mmol) in MeOH
(5 mL) was added aminothiocarbamide (11 mg, 0.1 mmol) and a solution of
dppeda (8 mg, 0.1 mmol) in CH2Cl2 (5 mL). The mixture was stirred for about 1 h
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D.-X. Li et al. / Inorganic Chemistry Communications 14 (2011) 1665–1668
300 MHz, ppm): δ 3.69 (d, 2H, \CH2-), 3.89 (d, 2H, \CH2-), 5.57 (s, 2H, \NH2),
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3144 (w), 2811 (w), 2362 (w), 1589 (m), 1522 (m), 1481 (m), 1434 (s), 1384 (w),
1184 (w), 1096 (w), 1027 (w), 999 (w), 852 (w), 741 (s), 695 (s), 505 (m), 431 (w).
1H NMR (CDCl3-d6, 300 MHz, ppm): δ 3.69(d, 2H, \CH2-), 3.89 (d, 2H, \CH2-), 5.57
(s, 2H, \NH2), 5.90 (s, 2H, \NH-), 7.26–7.33 (m, 20H, \Ph). 31P{1H} NMR
(300 MHz, ppm): δ −26.4 (s).
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[13] Crystal data for 1: C56H62Ag2O8N8P4S2, Mr=1378.9, colorless crystal, triclinic,
space group Pī, a=10.680(2) Å, b=11.703(2) Å, c=12.951(3) Å, α=74.33(3)°,
β=76.16(3)°, γ=75.99(3)°, V=1485.8(5) Å3, Z=1, Dc=1.541 g/cm3, F(000)=410