Oxidation of a one-dimensional coordination polymer and synthesis of the macrocyclic silver complex [Ag12(PhS2P-PS 2Ph)6(dppeS)6]

Article abstract of DOI:10.1002/ejic.200400738

The cluster chemistry with functionalised trimethylsilyl re-agents was investigated. The oxidation of the one-dimensional coordination polymer 1/ _∞[{Ag₂(PhS₂P-PS₂Ph)-dppe} ·dppe]_∞ leads to the formation of [Ag ₁₂(PhS₂-P-PS₂Ph)₆(dppeS) ₆] (dppeS = Ph₂P(CH₂)₂P(S)Ph ₂]. The dianionic ligand [PhPS₂-PS₂Ph] ^2- could possibly give rise to a new class of macrocyclic transition-metal chalcogenides. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.

Full text of DOI:10.1002/ejic.200400738

SHORT COMMUNICATION
Oxidation of a One-Dimensional Coordination Polymer and Synthesis of the
Macrocyclic Silver Complex [Ag12(PhS2P؊PS2Ph)6(dppeS)6]
Dieter Fenske,*[a] Alexander Rothenberger,[a] and Maryam Shafaei Fallah[a]
Keywords: Silver / Chalcogenides / Macrocycle / P ligands / S ligands
The cluster chemistry with functionalised trimethylsilyl re- ionic ligand [PhPS2−PS2Ph]2− could possibly give rise to a
agents was investigated. The oxidation of the one-dimen-
new class of macrocyclic transition-metal chalcogenides.
sional coordination polymer 1/ϱ[{Ag2(PhS2P−PS2Ph)-
dppe}·dppe]ϱ leads to the formation of [Ag12(PhS2-
P−PS2Ph)6(dppeS)6] (dppeS = Ph2P(CH2)2P(S)Ph2]. The dian-
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
Introduction
first result of these efforts and demonstrate the versatility
of the PϪS ligand [PhS2PϪPS2Ph]2Ϫ generated in the reac-
tion.
Over the last few years we have been investigating the
syntheses, structures and properties of a variety of silver-
chalcogen clusters including the phosphane-stabilised nano-
particle [Ag262S100(StBu)62(dppb)6] [dppb ϭ 1,4-bis(diphen-
ylphosphanyl)butane], which can be regarded as the largest
ligand-protected silver sulfide complex characterised so
far.[1] The general synthetic route to these species involves
Results and Discussion
By the reaction of AgOAc with dppe [dppe ϭ 1,2-bis(di-
the reaction of AgX (X ϭ halide, carboxylate) salts with phenylphosphanyl)ethane] and PhP(S)(SSiMe3)2 (Scheme 1),
tertiary phosphanes and subsequent reaction with trimeth- the one-dimensional coordination polymer 1/ϱ[{Ag2-
ylsilyl chalcogenides.[1] Recently, we continued with earlier (PhS2PϪPS2Ph)dppe}·dppe]ϱ (1) was obtained, and it was
work where we investigated the potential of reactions be- characterised by X-ray crystallography and 31P NMR spec-
tween the sulfur-functionalised phosphane P(S)(SSiMe3)3 troscopy (Figure 1).
and late transition metal salts for the building up of tran-
Analogous to the previously described reaction of
sition metal clusters with functionalised phosphane li- P(S)(SSiMe3)3, the formation of a PϪP bond was observed
gands.[2] A discovery made during these investigations was in reactions of AgOAc with PhP(S)(SSiMe3)2. In the solid-
that P(S)(SSiMe3)3 cannot be used as a source of [PS4]3Ϫ state structure of 1, the dianion [PhS2PϪPS2Ph]2Ϫ and one
anions. Instead
a
hexathiodiphosphonato tetraanion molecule of the neutral phosphane ligand dppe hold to-
[S3PϪPS3]4Ϫ is formed in reactions with late transition me- gether a tricyclic arrangement of two tetrahedrally coordi-
tal salts and this indicates that P(S)(SSiMe3)3 possibly nated Agϩ ions. An additional molecule of dppe completes
undergoes disproportionation into [(Me3SiS)2(S)PϪ the coordination sphere of the Ag atoms and acts as a
P(S)(SSiMe3)2], elemental sulfur and S(SiMe3)2.[2d,2e] This bridging ligand between the [Ag2(dppe)(PhS2PϪPS2Ph)]
reactivity prompted us to prepare new families of metal units (Figure 1). Bond lengths in 1 are within the range of
aggregates, which are accessible by the reaction of Ag2S commonly observed values.[4] SϪAgϪS bond angles in 1
with P2S5 or by heating mixtures of elemental Ag, P and [96.20(5) and 96.88(5)°] are similar to those observed in a
S.[3,4] Research in this area was motivated by the interest in bis(diphenylphosphanyl)methane adduct of a silver thiocar-
sulfide-based glasses and their use as solid electrolytes.[3] boxylate {SϪAgϪS [99.67(5)°]}.[5] It is worth noting that
For a wet-chemistry approach to these compounds, how- each S atom in 1 (coordination number: 2) coordinates one
ever, the use of solubilising organic groups is particularly Ag atom only, and the CϪPϪPϪC torsion angle in the
promising. We therefore chose the related silylated reagent [PhS2PϪPS2Ph]2Ϫ ligand is 50.2(4)°. A change of this tor-
PhP(S)(SSiMe3)2, tertiary phosphanes and silver acetate sion angle means alternative orientations of the S-donor
(AgOAc) as starting materials. Here we wish to report the centres in the ligand [PhS2PϪPS2Ph]2Ϫ, and this might
therefore result in different coordination modes of this li-
[a]
Institut für Anorganische Chemie, Universität Karlsruhe,
gand. Higher coordination numbers for the S-donor centres
Engesserstraße 15, Germany
were found in the related complex [Cu6(P2S6)Cl2(PPh3)6].[2b]
Fax: (internat.) ϩ49-(0)721-6088440
E-mail: dieter.fenske@chemie.uni-karlsruhe.de
X-ray structures of the closest related complexes of 1,
Eur. J. Inorg. Chem. 2005, 59Ϫ62
DOI: 10.1002/ejic.200400738
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
59

D. Fenske, A. Rothenberger, M. S. Fallah
SHORT COMMUNICATION
Scheme 1. Synthesis of 1 and oxidation leading to the formation of 2
Figure 1. Structure of a dppe-bridged [{PhPS2}2Ag2·dppe] unit in polymeric 1 (ellipsoids at 50%; connections to adjacent units are
˚
indicated; H atoms are omitted); selected bond lengths (A) and angles (°): AgϪS 2.556(2)Ϫ2.631(2), AgϪP 2.475(2)Ϫ2.510(2), PϪS
1.981(2)Ϫ1.992(2), P(1)ϪP(2) 2.262(3); CϪP(1)ϪP(2)ϪC 50.2(4), S(2)ϪAg(1)ϪS(4) 96.88(5), S(3)ϪAg(2)ϪS(1) 96.20(5), SϪAgϪP
103.89(6)Ϫ117.66(6), PϪPϪS 108.1(1)Ϫ108.8(1), S(1)ϪP(1)ϪS(2) 117.3(1), S(4)ϪP(2)ϪS(3) 116.0(1)
[M2(PhS2PϪPS2Ph)] (M ϭ Li, K), have to the best of our
Storage of a reaction mixture containing crystals of 1 at
room temperature for approximately three weeks produced
knowledge not yet been determined.[6]
In solutions of 1, two species, possibly rotamers, contain- colourless crystals of [Ag12(PhS2PϪPS2Ph)6(dppeS)6] (2)
ing PϪP bonds are present, which show two singlet reson- [dppeS ϭ Ph2P(CH2)2P(S)Ph2] (Scheme 1). Initially, this
ances at δ ϭ 84.4 and 81.2 ppm. A similar value (δ ϭ was realised because the amount of crystalline precipitate
85.4 ppm) is observed in the 31P NMR spectrum of in the reaction mixtures containing crystals of 1 increased,
[Li2(PhS2PϪPS2Ph)].[6b] The PϪP bond formation during and a closer look revealed that only crystalline blocks of 2
the preparation of 1 could be rationalized by the dispro- were present. Further experiments have shown that 2 can
portion of PhP(S)(SSiMe3)2 into [Ph(S)(SSiMe3)PϪP(S)- also be obtained by filtering off crystals of 1 and storage of
(SSiMe3)Ph], which instantly reacts with AgOAc, elemental the filtrate for several weeks. Mixtures of both 1 and 2 were
sulfur and S(SiMe3)2. The dppe ligands present in solution not observed. An X-ray analysis of 2 confirms the results
were oxidised to Ph2P(CH2)2P(S)Ph2 (δPϭS ϭ 45.6 ppm, from the 31P NMR spectra, in which indication for the for-
3JP,P ϭ 58 Hz).[7] In 1, the PIII centres of the dppe ligands mation of dppeS is found. As a consequence, oxidation-
and Ph2P(CH2)2P(S)Ph2 are identified by a broad singlet induced fragmentation of polymeric arrangements of 1
resonance (δ ϭ 0.6 ppm) (PϪAg coupling has not been re- gives rise to the macrocyclic complex 2 (Figure 2).
solved).[7,5] In order to gain further mechanistic insight and
Complex 2 crystallizes in the space group P1 with the
¯
to understand the formation of the [PhS2PϪPS2Ph]2Ϫ di- inversion centre located in the middle of the molecule.
anion we tried to synthesise the postulated intermediate di- Complex 2 is constructed from six corner-sharing distorted
˚
phenyltetrathiodiphosphonic acid trimethylsilyl ester AgS4 tetrahedra [AgϪS 2.553(3)Ϫ2.767(3)A, SϪAgϪS
[Ph(S)(SSiMe3)PϪP(S)(SSiMe3)Ph] in the absence of 89.4(1)Ϫ139.9(1)°] and forms a twelve-membered [AgS]6
AgOAc by the reaction of PhP(S)(SSiMe3)2 with dppe. ring (Figure 2). The six S atoms of the ring are located on
However, these attempts failed, and this indicates that PϪP the corners of an octahedron with nonbonding SϪS dis-
˚
bond formation only occurs in the presence of AgOAc.
tances of about 3.64Ϫ4.04 A. In the periphery, Ag(1) is co-
60
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2005, 59Ϫ62

Oxidation of a One-Dimensional Coordination Polymer
SHORT COMMUNICATION
[55.45(5)Ϫ58.59(5)°] is about 5Ϫ8° wider than that ob-
served in 1.
Conclusion
The ability of the [PhS2PϪPS2Ph]2Ϫ ligand to coordinate
in a variety of modes is demonstrated. Slight changes in the
CϪPϪPϪC torsion angle should allow access to a range
of new coordination modes with different arrangements of
polyhedral building blocks, for example, MS4 tetrahedra
(M ϭ Cu, Ag).[8] Further reactions currently under investi-
gation include metathesis reactions of 1 with metal halides
and the oxidation of 1 with elemental sulfur.
Experimental Section
General Remarks: All operations were carried out under purified
nitrogen. Dichloromethane was refluxed over calcium hydride, hep-
tane was dried with Na/benzophenone and freshly distilled. AgOAc
and dppe were purchased from Aldrich and used without further
purification. PhP(S)(SSiMe)2 was prepared by
a published
method.[9]
1: PhP(S)(SSiMe3)2 (0.50 g, 1.44 mmol) was added to a pale yellow
solution of AgOAc (0.24 g, 1.44 mmol) and dppe (0.57 g,
1.44 mmol) in dichloromethane (20 mL) at Ϫ40 °C. The solution
instantly became colourless, and the mixture was stirred for 2 h and
then warmed up to Ϫ10 °C. The reaction was kept at 0 °C for two
days. The solvent was then reduced to about 15 mL. Upon addition
of heptane (approximately 0.7 mL), a colourless precipitate was
formed, which redissolved when the mixture was shaken. After
storage of the solution at 0 °C for three weeks, colourless cuboc-
tahedral crystals of 1 were isolated. 31P NMR (101.256 MHz,
CDCl3, 25 °C, 65%H3PO4) δ ϭ 84.4, 81.2 (s, PhS2PϪPS2Ph),
0.8 ppm (br. s, Ph2PϪ), an additional resonance was observed at
3
δ
ϭ
45.0 ppm (d, JP,P
ϭ
60 Hz, Ph2P(CH2)2P(S)Ph2].
C
384H348Ag12P36S24: calcd. C 56.65, H 4.31; found C 57.03, H 3.92.
Figure 2. Molecular structure of 2 (H atoms are omitted) and struc-
ture of the core of 2 (C atoms and peripheral P and S atoms are
2: After formation of 1 (this was checked by determination of unit-
cell dimensions of a small sample), the reaction was stored for four
more weeks at 0 °C, and only blocks of 2 were isolated. Yield
0.41 g, 58% (based on AgOAc supplied; 2, excluding lattice-bound
CH2Cl2). M.p. 166Ϫ168 °C (decomposition into brown melt Ͼ172
°C). 31P NMR (121.485 MHz, CDCl3, 25 °C, 65% H3PO4): δ ϭ
˚
omitted; ellipsoids at 50%;); selected ranges of bond lengths (A)
and angles (°): AgϪS 2.535(3)Ϫ2.952(4), AgϪP 2.430(3)Ϫ2.449(3),
PϪP 2.261(4)Ϫ2.275(5), PϪS 1.988(4)Ϫ2.020(4), PϪSdppeS
1.955(5)Ϫ1.966(4); SϪAgϪS 87.5(1)Ϫ139.9(1), SϪAgϪP 91.1(1)Ϫ
132.6(1), PϪPϪS 104.1(2)Ϫ110.7(2), SϪPϪS 119.1(2)Ϫ120.0(2)
1
93.2, 89.4 (s, PhS2PϪPS2Ph), 82.0 and 79.4 (dd, JP,P ϭ 56 Hz,
PhS2PϪPS2Ph), 45.2 [br. m, Ph2P(CH2)2P(S)Ph2], 28.3 ppm [m,
3JP,P ϭ 59 Hz, Ph2P(CH2)2P(S)Ph2] coupling to 107/109Ag could not
be identified unequivocally, Ph2P(CH2)2P(S)Ph2. IR (CsI, Nujol):
ν˜ ϭ 1439 (PϪPh), 690, 612 (PϭS), 579, 508, 466 cmϪ1 (tentatively
assigned as PϪP and PϪS). MS (Maldi TOF), m/z (%) ϭ 538.39
(30) [dppeSAgϩ], 430.61 (100) [dppeSϩ], 398.69 (8) [dppeϩ].
C228H204Ag12P24S30 (5943.7): calcd. C 46.07, H 3.46; found C
46.05, H 3.50.
ordinated by S atoms of two different AgS4 tetrahedra,
whilst Ag(4) and Ag(6) are located over the edges of the
central AgS4 units. One S atom of each [PhS2PϪPS2Ph]2Ϫ
ligand is not part of the [Ag6S18] core and completes the
tetrahedral coordination sphere of the outer Ag atoms, to-
gether with one P atom of the monodentate dppeS ligands
(Figure 2). Signals for the chemically non-equivalent P
atoms in the [PhS2PϪPS2Ph]2Ϫ ligand in 2 can be observed
in the 31P NMR spectrum (AB spin system; two doublet
resonances at δ ϭ 82.0 and 79.4 ppm, 1JP,P ϭ 56 Hz). In the
Maldi TOF-MS the ions [Ag(dppeS)]ϩ, [dppe]ϩ and
[dppeS]ϩ were detected. The coordination numbers of the
S atoms in 2 are greater than those in the solid-state struc-
X-ray Crystallography: Data were collected with a STOE STADI 4
diffractometer equipped with a CCD detector (1) and with a Stoe
IPDS II diffractometer (2) using graphite-monochromated Mo-Kα
˚
radiation (λ ϭ 0.71073 A). The structures were solved by direct
methods and refined by full-matrix least-squares on F2 (all data)
with the SHELXTL program package.[10] Hydrogen atoms were
ture of 1, and also the CϪPϪPϪC torsion angle in 2 placed in calculated positions, non-hydrogen atoms were assigned
Eur. J. Inorg. Chem. 2005, 59Ϫ62
www.eurjic.org © 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 61

D. Fenske, A. Rothenberger, M. S. Fallah
SHORT COMMUNICATION
anisotropic thermal parameters, atoms of lattice-bound solvent
ancial support. Thanks are also due to Dr. O. Fuhr (Forschungsz-
molecules were refined with isotropic thermal parameters. In order entrum Karlsruhe) for recording MALDI-TOF spectra.
to identify further possible by-products unit-cell dimensions of
crystals from different samples were repeatedly determined, and in
each case, at first 1 and then 2, were obtained as the only products
that we were able to characterise.
[1]
D. Fenske, C. Persau, S. Dehnen, C. E. Anson, Angew. Chem.
2004, 116, 309Ϫ313 and references cited therein.
Crystal Data for 1·8C7H16·6CH2Cl2: C384H348Ag12P36S24 (eight
heptane and six CH2Cl2 solvent molecules per formula unit), M ϭ
8141.93; trigonal, space group R3; Z ϭ 3; a ϭ b ϭ 31.214(4), c ϭ
[2]
For transition metal clusters containing PϪP bonded PϪS/Se
[2a]
ligands see, for example.
C. W. Liu, C.-M. Hung, B. K.
¯
Santra, J.-C. Wang, H.-M. Kao, Z. Lin, Inorg. Chem. 2003, 42,
3
˚
˚
8551Ϫ8556. [2b] C. W. Liu, H.-C. Chen, J.-C. Wang, T.-C. Keng,
40.099(8) A; V ϭ 33835(10) A ; T ϭ 197(2) K; F(000) ϭ 14568;
Dcalcd. ϭ 1.392 gcmϪ3. 59537 reflections collected, of which 19049
were unique (Rint ϭ 0.0615). 771 parameters; final wR2 ϭ 0.2367
(all data); R1 ϭ 0.0727 {I Ͼ 2σ(I)}; largest difference peak and
Angew. Chem. 2001, 113, 2404Ϫ2406, Angew. Chem. Int. Ed.
[2c]
2001, 40, 2342Ϫ2344.
K. Chondroudis, D. Chakrabarty, E.
A. Axtell, M. G. Kanatzidis, Z. Anorg. Allg. Chem. 1998, 624,
975Ϫ979. [2d] S. Wirth, D. Fenske, Z. Anorg. Allg. Chem. 1999,
625, 2064Ϫ2070. [2e] F. Weigend, S. Wirth, R. Ahlrichs, D. Fen-
ske, Chem. Eur. J. 2000, 6, 545Ϫ551.
Ϫ3
˚
hole 2.834, Ϫ0.947 e·A
.
Crystal Data for 2·18CH2Cl2: C228H204Ag12P24S30 (eighteen
CH2Cl2 solvent molecules per formula unit) M ϭ 5943.83; triclinic,
[3]
[4]
Z. Zhang, J. H. Kennedy, H. Eckert, J. Am. Chem. Soc. 1992,
114, 5775Ϫ5784 and references cited therein.
¯
space group P1; Z ϭ 1; a ϭ 19.281(4), b ϭ 20.329(4), c ϭ 22.806(5)
˚
˚
˚
3
PϪP 2.267(5) A, PϪS ca. 2.0 A, AgϪS 2.528(5)Ϫ2.942(5) A
in Ag4P2S6: P. Toffoli, P. Khodadad, N. Rodier, Acta Crys-
tallogr., Sect. C 1983, 39, 1485Ϫ1488.
˚
˚
A; α ϭ 96.20(3), β ϭ 114.11(3), γ ϭ 108.83(3)°; V ϭ 7419(3) A ;
T ϭ 130(2) K; F(000) ϭ 3732; Dcalcd. ϭ 1.672 gcmϪ3. 43858 reflec-
tions measured, of which 24516 were unique (Rint ϭ 0.0860). 1432
parameters; final wR2 ϭ 0.2395 (all data); R1 ϭ 0.0859 {I Ͼ 2σ(I)};
[5]
T. C. Deivaraj, J. J. Vittal, J. Chem. Soc., Dalton Trans. 2001,
322Ϫ328.
Ϫ3
˚
[6] [6a]
[6b]
largest difference peak and hole 2.457, -2.055 e·A
.
E. Fluck, H. Binder, Angew. Chem. 1967, 79, 903.
A.
Schmidpeter, K.-H. Zirkow, Phosphorus and Sulfur 1988, 36,
CCDC-243898 and CCDC-243899 contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or
from the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB2 1EZ, UK; Fax: (internat.) ϩ44-1223-336-
033; E-mail: deposit@ccdc.cam.ac.uk].
15Ϫ21.
[7]
[8]
E. I. Matrosov, Z. A. Starikova, A. I. Yanovsky, D. I. Lobanov,
I. M. Aladzheva, O. V. Bykhovskaya, Y. T. Struchkov, T. A.
Mastryukova, M. I. Kabachnik, J. Organomet. Chem. 1997,
535, 121Ϫ127.
S. Dehnen, A. Eichhöfer, D. Fenske, Eur. J. Inorg. Chem.
2002, 279Ϫ317.
[9]
J. Hahn, T. Nataniel, Z. Anorg. Allg. Chem. 1986, 543, 7Ϫ21.
G. M. Sheldrick, SHELXTL-97, Program for Crystal Structure
Determination, University of Göttingen, Germany, 1997.
Received September 2, 2004
Acknowledgments
We gratefully acknowledge the DFG (Zentrum für funktionelle
Nanostrukturen) and the Fonds der Chemischen Industrie for fin-
[10]
62
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2005, 59Ϫ62