Synthesis and characterization of organophosphine/phosphite stabilized silver(I) methanesulfonates: Crystal structures of [Ph3PAgO3SCH3] and [(Ph3P)2AgO3SCH3]

Article abstract of DOI:10.1016/j.poly.2008.04.041

Six organophosphine/phosphite stabilized silver(I) methanesulfonates of type [L_nAgO₃SCH₃] (L = Ph₃P, n = 1, 2a; n = 2, 2b; n = 3, 2c; L = (EtO)₃P; n = 1, 2d; n = 2, 2e; n = 3, 2f) were synthesized by the reaction of silver methanesulfonates with triphenylphosphine or triethylphosphite in dichloromethane under nitrogen atmosphere. These complexes were obtained in high yields and characterized by elemental analysis, ¹H-, ¹³C{H} NMR, IR spectroscopy and thermogravimetric analysis (TGA), respectively. X-ray single crystal analysis reveals that complex 2a is a tetramer [Ph₃PAgO₃SCH₃]₄ and complex 2b is a monomer. The thermal stability of 2a has been studied by applying thermogravimetric analysis. It starts to decompose between 50 and 440 °C in a three-step process. The final residue (Ag) is about 20.50%.

Full text of DOI:10.1016/j.poly.2008.04.041

Polyhedron 27 (2008) 2501–2505
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Synthesis and characterization of organophosphine/phosphite stabilized silver(I)
methanesulfonates: Crystal structures of [Ph3PAgO3SCH3] and [(Ph3P)2AgO3SCH3]
*
Yi-Ying Zhang, Yan Wang, Xian Tao, Ning Wang, Ying-Zhong Shen
Applied Chemistry Department, School of Material Science and Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Six organophosphine/phosphite stabilized silver(I) methanesulfonates of type [LnAgO3SCH3] (L = Ph3P,
n = 1, 2a; n = 2, 2b; n = 3, 2c; L = (EtO)3P; n = 1, 2d; n = 2, 2e; n = 3, 2f) were synthesized by the reaction
of silver methanesulfonates with triphenylphosphine or triethylphosphite in dichloromethane under
nitrogen atmosphere. These complexes were obtained in high yields and characterized by elemental anal-
ysis, 1H-, 13C{H} NMR, IR spectroscopy and thermogravimetric analysis (TGA), respectively. X-ray single
crystal analysis reveals that complex 2a is a tetramer [Ph3PAgO3SCH3]4 and complex 2b is a monomer.
The thermal stability of 2a has been studied by applying thermogravimetric analysis. It starts to decom-
pose between 50 and 440 °C in a three-step process. The final residue (Ag) is about 20.50%.
Ó 2008 Elsevier Ltd. All rights reserved.
Received 24 November 2007
Accepted 27 April 2008
Available online 14 June 2008
Keywords:
Silver(I) methanesulfonates
Organophosphine
Thermogravimetric analysis
Crystal structure
1. Introduction
the radical decomposition mechanism. But to the best of our
knowledge, Lewis-base stabilized silver methanesulfonates have
Silver(I) complexes have been widely studied because they have
shown a great tendency to form rich structure characteristics [1–
6], potential application in catalysis [7] and material science
[8,9]. Lewis-base stabilized silver(I) complexes have recently at-
tracted renewed interests, mostly because of their application as
precursors in the growth of silver thin films via chemical vapor
deposition (CVD) techniques, which could be used as new inter-
connect material for the future generations of deep submicro inte-
grated circuits because of the lower resistivity and superior
electromigration resistance [10–15].
not been reported until now. In order to search for the new kind
of silver precursor used in CVD technique, a series of organophos-
phine stabilized silver(I) sulfonates, [LnAgO3SCH3] (L = Ph3P, n = 1,
2a; n = 2, 2b; n = 3, 2c; L = (EtO)3P; n = 1, 2d; n = 2, 2e; n = 3, 2f),
were synthesized and characterized. The single crystal structures
of 2a and 2b were determined and discussed. The thermal stability
of 2a has been studied by applying thermogravimetric analysis
(TGA) has been studied as well.
2. Experimental
The key to achieve success for CVD, however, is the selection of
suitable precursors. As the precursor for CVD, the complexes
should have: (i) suitable vapor pressure for transporting it from
bubbler to CVD reactor; (ii) suitable thermal decomposition mech-
anism, (iii) suitable thermal stability which means that it could not
decompose during the transportation but decompose easily in the
reactor [16,17]. Several organic molecules have been often used as
ligands to synthesize the silver complexes, such as b-diketonate
and its analogous as the main ligands [18,19], and phosphines as
ancillary ligands [20,21]. For example, [(CH3)3CCOCHCOC3F7Ag-
PEt3] [22], [(fod)3Ag(PPh3)5] [23] were reported to be successfully
used as precursors for the silver film deposition. Lewis-base
stabilized silver carboxylates such as [Ph3PAgO2CR] [24],
[(Ph3P)2AgO2CC3F7] [25] are another kind of precursors for silver
deposition due to the higher utility of silver (100%) according to
2.1. General procedure
All operations were carried out under an atmosphere of purified
nitrogen with standard Schlenk techniques. The solvent dichloro-
methane (CH2Cl2) was purified by distillation from P2O5 under
N2. The AgO3SCH3 was synthesized by reacting CH3SO3H with
excessive Ag2CO3 in water. 1H NMR were recorded on a Bruker
Avance 300 spectrometer operating at 300.130 MHz in the Fourier
transform mode; 13C{H} NMR spectra were recorded at
75.467 MHz. Chemical shifts are reported in d units (parts per mil-
lion) downfield from tetramethylsilane (d = 0.0 ppm) with the sol-
vent as the reference signal (1H NMR, CDCl3 d = 7.26; 13C{H} NMR,
CDCl3 d = 77.55). Infrared spectra were collected on Bruker Vector
22 at room temperature. Elemental analyses were performed on
a Perkin–Elmer 240C elemental analyzer. Melting points were ob-
served in sealed capillaries and were uncorrected. Thermogravi-
metric analysis were performed on a American TA2000/2960
* Corresponding author. Tel.: +86 25 52112904 84765; fax: +86 25 52112626.
E-mail address: yz_shen@nuaa.edu.cn (Y.-Z. Shen).
0277-5387/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2008.04.041

2502
Y.-Y. Zhang et al. / Polyhedron 27 (2008) 2501–2505
analyzer with a heating rate of 10 °C minÀ1 under nitrogen
atmosphere.
CH3CH2–). 13C{H} NMR (CDCl3): d 39.2 (CH3), 16.6 (JPC = 6.5 Hz,
CH3/CH3CH2–), 61.4 (JPC = 3.1 Hz, CH2/CH3CH2–). IR (KBr) data
(cmÀ1): 2981 (s), 2929 (m), 2900 (m), 1477 (m), 1444 (m), 1391
(m), 1244 (s), 1207 (s), 1152 (vs), 1095 (m), 1015 (vs), 942, (vs),
764 (vs), 555 (s).
2.2. Synthesis
2.2.1. Synthesis of CH3SO3Ag (1)
Methane sulfonic acid (5 g, 0.052 mol) dissolved in 50 mL of
H2O was added dropwise into a stirred suspended solution of
[Ag2CO3] (8.7 g, 0.031 mol) in 20 mL of H2O at 20 °C. The clear solu-
tion was obtained by filtration through a pad of celite after stirring
the reaction mixture for 1 h at 20 °C. A white solid product was ob-
tained after removing water in Rotary Evaporator and Vacuum
Drying Oven at 50 °C. The product was stored under nitrogen and
keep in dark place. Yield: 8.8 g (83%, based on Ag2CO3).
2.2.6. Synthesis of [(EtO)3P]2AgO3SCH3 (2e)
Complex 2e was synthesized following the synthesis of 2a (Sec-
tion 2.2.1). In this respect, [(EtO)3P] (1.4231 g, 8.57 mmol) was re-
acted with [AgO3SCH3] (0.8700 g, 4.285 mmol). After appropriate
work-up (see Section 2.2.1), complex 2e was obtained as a colour-
less liquid. Yield: 2.09 g (91%, based on AgO3SCH3). Anal. Calc. for
C
13H33O9AgP2S: C, 29.17; H, 6.21. Found: C, 29.03; H, 6.22%. 1H
NMR (CDCl3): d 1.2 (t, 18H, CH3/CH3CH2–, JHH = 7.0), 2.7 (s, 3H),
4.0 (m, 12H, CH2/CH3CH2–). 13C{H} NMR (CDCl3): d 39.2 (CH3),
16.7 (JPC = 5.6 Hz, CH3/CH3CH2–), 61.3 (JPC = 2.2 Hz, CH2/CH3CH2–
). IR (KBr) data (cmÀ1): 2981 (s), 2934 (m), 2904 (m), 1478 (m),
1444 (s), 1388 (m), 1238 (s), 1208 (s), 1163 (s), 1098 (m), 1020
(vs), 939 (vs), 768 (vs), 531 (s).
2.2.2. Synthesis of Ph3PAgO3SCH3 (2a)
Triphenylphosphine (0.1318 g, 0.5 mmol) dissolved in 20 mL of
CH2Cl2 was added dropwise into a stirred suspended solution of
[CH3SO3Ag] (0.1020 g, 0.5 mmol) in 20 mL of CH2Cl2 at 0 °C. The
clear solution was obtained by filtration through a pad of celite
after stirring the reaction mixture for 6 h at 0 °C. A white solid
product was obtained after removing all the volatiles in oil-pump
vacuo, yield: 0.21 g (91%, based on CH3SO3Ag). M.p.: 187 °C dec.
Anal. Calc. for C19H18O3AgPS: C, 49.05; H, 3.90. Found: C, 48.93;
H, 3.85%. 1H NMR (CDCl3): d 2.8 (s, 3H, CH3–H), 7.4–7.6 (m, 15H,
Ph–H). 13C{H} NMR (CDCl3): d 39.1 (CH3), 134.3 (JPC = 16.0 Hz,
C6H5), 132.3 (JPC = 22.4 Hz, C6H5), 131.4 (C6H5), 129.6
(JPC = 10.36 Hz, C6H5). IR (KBr) data (cmÀ1): 3051 (m), 2962 (m),
1476 (m), 1435 (s), 1388 (m), 1258 (s), 1196 (vs), 1093 (vs),
1023 (vs), 804 (s), 740 (s), 692 (vs), 507 (s).
2.2.7. Synthesis of [(EtO)3P]3AgO3SCH3 (2f)
Complex 2f was synthesized following the synthesis of 2a (Sec-
tion 2.2.1). In this respect, [(EtO)3P] (1.5644 g, 9.4 mmol) was re-
acted with [AgO3SCH3] (0.6337 g, 3.1 mmol). After appropriate
work-up, complex 2f can be isolated as a colourless liquid. Yield:
2.06 g (93%, based on AgO3SCH3). Anal. Calc. for C19H48O12AgP3S:
C, 32.53; H, 6.90. Found: C, 32.33; H, 6.72%. 1H NMR (CDCl3): d
1.2 (t, 27H, CH3/CH3CH2–, JHH = 7.0), 2.6 (s, 3H), 4.0 (m, 18H, CH2/
CH3CH2–). 13C{H} NMR (CDCl3): d 39.2 (CH3), 16.6 (JPC = 5.8 Hz,
CH3/CH3CH2–), 60.8 (JPC = 3.4 Hz, CH2/CH3CH2–). IR (KBr) data
(cmÀ1): 2982 (vs), 2934 (s), 2902 (m), 1477 (m), 1444 (m),
1391(s), 1241 (s), 1209 (s), 1161 (s), 1098 (m), 1022 (vs), 941
(vs), 764 (vs), 531 (s).
2.2.3. Synthesis of (Ph3P)2AgO3SCH3 (2b)
Complex 2b as a white solid was obtained following the above
procedure, only using [CH3SO3Ag] (0.1401 g, 0.69 mmol) and tri-
phenylphosphine (0.3621 g, 1.38 mmol) instead. Yield: 0.477 g
(95%, based on AgO3SCH3). M.p.: 195 °C dec. Anal. Calc. for
2.3. Single crystal structures of Ph3PAgO3SCH3 (2a) and
(Ph3P)2AgO3SCH3 (2b)
C
37H33O3AgP2S: C, 61.08; H, 4.57. Found: C, 60.87; H, 4.54. 1H
NMR (CDCl3): d 2.6 (s, 3H, CH3), 7.2–7.4 (m, 30H, Ph). 13C{H}
NMR (CDCl3): d 39.1 (CH3), 134.4 (JPC = 13.3 Hz, C6H5), 132.3
(JPC = 22.3 Hz, C6H5), 130.9 (C6H5), 129.4 (JPC = 10.36 Hz, C6H5). IR
(KBr) data (cmÀ1): 3053 (m), 2959 (m), 1476 (m), 1435 (s), 1392
(m), 1263 (s), 1200 (vs), 1095 (vs), 1039 (vs), 804 (m), 749 (s),
696 (vs), 507 (s).
Single crystals of 2a and 2b could be obtained by cooling a
saturated dichloromethane solution to À30 °C. Suitable crystals
for X-ray determination were placed in glue under N2 for they
are sensitive to moisture and oxygen. The crystal structure data
collection was done on a BRUKER SMART APEX CCD diffractometer
using graphite monochromatic Mo Ka radiation (k = 0.71073 Å) at
room temperature. The program SMART [26] was used for determi-
nation of the unit cell. Data reduction and integration was carried
out with SAINT [26] and absorption corrections were applied using
the program SADABS [27]. The structure was solved using direct
methods and refined by full-matrix least-squares procedures on
F2 (SHELX-97 [28]). All of the non-hydrogen atoms were refined with
anisotropic displacement parameters. Crystallographic data and
details on refinement are presented in Table 1. The crystal struc-
tures of 2a and 2b are drawn using ORTEP [29].
2.2.4. Synthesis of (Ph3P)3AgO3SCH3 (2c)
Complex 2c was synthesized following the synthesis of 2a (Sec-
tion 2.2.1). In this respect, triphenylphosphine (0.4388 g,
1.67 mmol) was reacted with [AgO3SCH3] (0.1132, 0.558 mmol).
After appropriate work-up (see Section 2.2.1), complex 2c was ob-
tained as a white solid. Yield: 0.51 g (93%, based on AgO3SCH3]).
M.p.: 215.2 °C dec. Anal. Calc. for C55H48AgO3P3S: C, 66.74; H,
4.89. Found: C, 66.47; H, 4.62%. 1H NMR (CDCl3): d 2.5 (s, 3H,
CH3), 7.2–7.4 (m, 45H, Ph). 13C{H} NMR (CDCl3): d 39.4 (CH3),
134.2 (JPC = 16.06 Hz, C6H5), 132.3 (JPC = 23.29 Hz, C6H5), 130.7
(C6H5), 129.3 (JPC = 9.24 Hz, C6H5). IR (KBr) data (cmÀ1): 3051
(m), 2959 (m), 1480 (m), 1435 (s), 1387 (m), 1260 (s), 1196 (vs),
1087 (s), 1035 (vs), 804 (m), 749 (s), 696 (vs), 507 (s).
3. Results and discussion
3.1. Synthesis
2.2.5. Synthesis of (EtO)3PAgO3SCH3 (2d)
The phosphine/phosphite stabilized silver(I) methanesulfonates
(L = Ph3P, n = 1, 2a; n = 2, 2b; n = 3, 2c; L = (EtO)3P; n = 1, 2d; n = 2,
2e; n = 3, 2f) were prepared by using Ph3P/(EtO)3P reacting with
solver(I) methanesulfonate in dichloromethane in stoichiometry
at 0 °C under nitrogen atmosphere in high yield (Scheme 1). The
complexes were isolated as white solids (2a–2c) or colourless
liquids (2d–2f). They are very sensitive to temperature, moisture,
oxygen as well as light. The complexes are insoluble in cold
Complex 2d was synthesized following the synthesis of 2a (Sec-
tion 2.2.1). In this respect, [(EtO)3P] (1.88 g, 11.32 mmol) was re-
acted with [AgO3SCH3] (2.29 g, 11.32 mmol). After appropriate
work-up, complex 2d can be isolated as a colourless liquid. Yield:
3.77 g (90%, based on AgO3SCH3). Anal. Calc. for C7H18O6AgPS: C,
22.78; H, 4.92. Found: C, 22.67; H, 4.78%. 1H NMR (CDCl3): d 1.2
(t, 9 H, CH3/CH3CH2–, JHH = 7.0), 2.8 (s, 3 H), 4.0 (m, 6H, CH2/

Y.-Y. Zhang et al. / Polyhedron 27 (2008) 2501–2505
2503
À1
Table 1
Crystallographic data and structure refinement details for 2a and 2b
and 1180–1200 cm
can be interpreted as the asymmetric and
symmetric vibration of SO2, which is the similar as previous reported
[33–37]. The absorptions around 1030 cmÀ1 can be assigned as
vibration of S–O; which is similar to the reported value [33–37].
The NMR spectra (1H and 13C{H}) were recorded for all six com-
plexes (see Section 2) at room temperature, In 1H NMR, the proton
spectra were consistent with the stoichiometries of the complexes.
The protons of complexes 2a–2c in the aryl proton region of the 1H
NMR spectra were in the range of 7.2–7.6 ppm. The complexes
(2d–2f) are easily distinguished because the resonances of the pro-
tons show only two groups. The proton of CH3 – in CH3SO3 – ap-
peared at 2.6–2.8 ppm, which agrees with previous reported [23].
In the 13C{H} NMR spectra of 2a–2c the triphenylphosphine carbon
resonances are easily distinguished (in the range of 129.6–
134.2 ppm). The carbon resonance of CH3 – on CH3SO3 – shows
in the lower field (39.1–39.4 ppm) comparing to that of [(EtO)3P]
(ca. 16.7 ppm).
Compound
2a
2b
Formula
C
80H80Ag4Cl8O12P4S4
C38H35AgCl2O3P2S
812.43
0.5 Â 0.5 Â 0.6
monoclinic
P21/c
9.381(1)
20.165(1)
19.653(1)
90.00
92.58
90.00
3714.1(4)
4
1.453
À10 6 h 6 11,
À13 6 k 6 25,
À24 6 l 6 24
1656
0.864
0.71073
293
Formula weight
Crystal dimensions (mm)
Crystal system
Space group
a (Å)
2200.64
0.4 Â 0.5 Â 0.6
tetragonal
I41/a
23.993(1)
23.993(1)
15.702(1)
90.00
90.00
90.00
9039.2(8)
4
1.617
À26 6 h 6 30,
À30 6 k 6 30,
À17 6 l 6 19
4416
1.309
0.71073
293
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V [Å3]
Z value
Dcalc (g/cm3)
Index ranges
F(000)
l
(Mo K
a
a
) (mmÀ1
) (Å)
)
3.2. Single crystal structure of 2a and 2b
k (Mo K
Temperature (K)
The X-ray single crystal analysis results indicate that the molec-
ular formula of complex 2a is [(Ph3PAgO3SCH3)4 Á 4CH2Cl2] and
complex 2b is [(Ph3P)2AgO3SCH3 Á CH2 Cl2]. Because of different
molar ratio of triphenylphosphine with silver methylsulofonate,
complex 2b is a monomer with each silver atom coordinated by
two PPh3 groups. Complex 2a, however, is a tetramer with the sil-
ver atom coordinated by one PPh3 group. The molecular structure
of 2a and 2b are depicted in Fig. 1 and Fig. 2, and selected bond dis-
tances (Å) and bond angles (°) are given in Table 2.
Complex 2a crystallizes in the tetragonal with space group I41/
a, which is composed of a tetramer [Ph3PAgO3SCH3]4 and four mol-
ecules of dichloromethane, as shown in Fig. 1. This is different from
the reported complex [Ph3PAgO3SCF3] which exists as a trimer
[38]. In the tetramer complex, the Ag4O4 core of the molecule is re-
garded as a ‘‘cubane-like” framework, with the alternate corners of
the cube occupied by the silver atoms and the methanesulfonic
oxygen atoms. The phosphorous atoms are approximately apical,
2hmax (°)
Number of reflections
measured
Independent reflections
observed [I > 2r(I)]
Number of refined
parameters
54
4934
54
7992
4568
254
6687
433
R1 [I > 2
wR2 [I > 2
Goodness-of-fitc
r
(h)]a
(h)]b
0.0901
0.1592
1.068
1.01
0.0624
0.1472
1.168
0.71
r
D
D
qmax (e ÅÀ3
)
qmin (e ÅÀ3
)
À0.61
À0.51
P
P
P
P
a
R1
w2a = 1/[
=
(||Fo| À |Fc||)/ |Fo|; wR2 = [ (w(F2o À Fc2)2)/ (wFo4)]1/2
.
b
r
2(F2o) + (0.0038P)2 + 166.3623P],
P = (F2o + 2Fc2)/3.w2b = 1/[
r
2(F2o) +
(0.0485P)2 + 3.1225P], P = (Fo2 + 2F2c)/3.
P
S = [ w(F2o À F2c)2]/(n À p)1/2, n = number of reflections, p = parameters used.
c
CH2Cl2
LnAgO3SCH3
CH3SO3Ag + nL
1
2a - 2f
L = Ph3P;
n = 1 (2a)
n = 2 (2b)
n = 3 (2c)
L = (EtO)3P; n = 1 (2d)
n = 2 (2e)
n = 3 (2f)
Scheme 1. Synthesis of complexes 2a–2f.
non-polar solvent like petroleum, whereas they are highly soluble
in polar or unsaturated hydrocarbons such as methylenechloride,
benzene. All the obtained products gave satisfactory elemental
analysis results, which were characterized by elemental analysis,
IR, 1H NMR, 13C{H} NMR, respectively.
As we know, the typical group vibration of sulfonates shows in
the range of 1350–1050 cmÀ1 [30,31]. When the R—SO3 anion is
À
‘‘free”, that is to say, non-coordinated, it shows local C3v-symmetry
with two mso bands for the symmetrical. Upon coordination to a
metal, the C3v-symmetry is broken and for a Cs-symmetrical R–
SO2–O–M moiety and three mSO bands are observed (
m
as(SO2);
m
s(SO2);
m
(S–O)). In the case of lithium and sodium salt of the
methanesulfonate anion (CH3SO3À), the as(SO2); s(SO2) are ob-
m m
served at 1233 and 1060 cmÀ1, respectively (for the NaO3SCH3)
as
and
m
(1244 cmÀ1); m(sSO2) (1185 cmÀ1); m(S–O) (1050 cmÀ1) for
(SO2)
LiO3SCH3 [32]. In the IR spectra of 2a–2f it shows prominent absorp-
Fig. 1. ORTEP drawing of 2a, showing 30% probability displacement ellipsoids. The
hydrogen atoms and solvent molecules are omitted for clarity.
tions in vSO3 region. The absorptions in the range of 1238–1268 cmÀ1

2504
Y.-Y. Zhang et al. / Polyhedron 27 (2008) 2501–2505
100
80
60
40
20
0
100
200
300
400
500
600
Temperature (oC)
Fig. 3. TG trace of 2a (heating rate of 10 °C minÀ1, nitrogen atmosphere).
2.552(3) Å] are much shorter than those [2.775(2), 2.854(2) Å] of
[(MePh2P)2AgO3SCF3] [42] and much longer than those in complex
2a [2.389(5), 2.449(5), 2.465(5) Å]. The P–Ag–P angle [132.4(4)°] is
much smaller than that [156.2(3)°] of [(MePh2P)2AgO3SCF3] [42],
respectively.
Fig. 2. ORTEP drawing of 2b, showing 30% probability displacement ellipsoids. The
hydrogen atoms and solvent molecules are omitted for clarity.
Table 2
Selected bond distances (Å) and angles (°) for 2a and 2b
3.3. Thermogravimetric analysis (TGA)
Complex 2a
Ag(1)–P(1)
2.348(2)
2.465(5)
Ag(1)–O(1)
Ag(1)–O(1)c
2.389(5)
2.449(5)
Ag(1)–O(1)b
Thermogravimetric analysis (Fig. 3) was carried-out to deter-
mine the relative volatility and evaluate the suitability of complex
as possible CVD precursors. These studies are also required to opti-
mize the temperature at which the respective single silver precur-
sor should be maintained during the CVD experiments. Complex
2a, for example, decomposes between 50 and 440 °C in a three-
step process. The first step takes place between 50 and 105 °C with
the 10.97% weight loss, the second step is observed in the range of
105–370 °C with the 58.43% weight loss, and the third step is be-
tween 370–440 °C with the 10.10% weight loss. The total weight
loss is 79.50%. These data show that the percentage of the residue
is 20.50% (Ag), which is close to the theoretical value of silver
(23.18%) in complex 2a. The real thermal decomposition mecha-
nism of complex 2a and other complexes would be studied in
the further research.
P(1)–Ag(1)–O(1)
P(1)–Ag(1)–O(1)c
O(1)–Ag(1)–O(1)c
Ag(1)–O(1)–Ag(1)a
Ag(1)–O(1)–Ag(1)b
135.5(1)
130.8(1)
78.5(2)
102.5(2)
98.7(2)
P(1)–Ag(1)–O(1)b
O(1)–Ag(1)–O(1)b
O(1)b–Ag(1)–O(1)c
Ag(1)a–O(1)–Ag(1)b
133.0(1)
79.5(2)
77.1(2)
100.3(2)
Complex 2b
Ag(1)–P(1)
Ag(1)–O(1)
2.434(1)
2.501(3)
Ag(1)–P(2)
Ag(1)–O(2)
2.422(1)
2.552(3)
P(1)–Ag(1)–P(2)
P(1)–Ag(1)–O(2)
P(2)–Ag(1)–O(2)
132.4(4)
108.9(8)
118.3(8)
P(1)–Ag(1)–O(1)
P(2)–Ag(1)–O(1)
O(1)–Ag(1)–O(2)
104.0(8)
106.6(8)
56.5(1)
Symmetry code: a = 5/4 À y, 1/4 + x, 9/4 À z; b = 1 À x, 3/2 À y, z; c = À1/4 + y,
5/4 À x, 9/4 À z.
coordinating to the silver atom, thereby completing a distorted tet-
rahedral coordination arrangement of the silver atom. The angles
of O–Ag–O [79.5(2)°, 77.1(2)°, 78.5(2)°] and Ag–O–Ag [100.7(2)°,
102.5(2)°, 98.7(2)°] are close to 90°, but the former are smaller
than the latter, which confirms the deformation of the ‘‘cubane”
just like other ‘‘cubane-like” complexes [39,40]. The P–Ag distance
(2.348(2) Å) is close to the sum of covalent radio of P and Ag atoms
(2.44 Å) [39] and slightly shorter than other complexes [(Ph3P)2Ag
(O2CC3F7)] 2.406(1) Å [24], [(Ph3P)3Ag(OPhMe2)], 2.539(2) Å [41].
Complex 2b crystallizes in the tetragonal with space group P 21/c
and exists as a monomer with a molecule of dichloromethane in
crystal structure (show in Fig. 2). The silver atom is coordinated
by two phosphorus atoms of triphenylphosphine and two
methanesulfonic oxygen atoms at the same time. This coordination
mode is similar to the reported complex [(MePh2P)2AgO3SCF3]
[42] and several silver(I) carboxylates such as [(Ph3P)2Ag
(O2CCH@CHCH2CH2CH3)] [24] and [(Ph3P)2Ag(CO2CF3)], but
different from the reported complex [(Ph3P)2AgO3SCF3] [42] which
exists as a dimmer. The distances of Ag–P [2.422(1), 2.434(1) Å] are
longer than that of [(R3P)2AgO3SCF3] [2.385(8), 2.389(8) Å] and
complex 2a [2.348(2) Å]. The Ag–O distances [2.501(3),
4. Supplementary data
CCDC 656251 and 666194 contain the supplementary crystallo-
graphic data for 2a and 2b. 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.
Acknowledgements
We gratefully acknowledge National 863 Research Project
(2006AA03Z219), Natural Science Foundation of Jiangsu province
(BK2007199); Foundation for ‘‘Liu Da Ren Cai” of Jiangsu Province
(06-E-021), the Excellent Project for the Returned Oversea Chinese
Scholars, National Defense Industry Committee (R0563-062) and
State Education Ministry (N0502-062). The State Postdoctoral
Foundation of China (No. 2006040932), the Postdoctoral Founda-
tion of Jiangsu Province (No. 0602008B) and Foundation from
NUAA are also acknowledged.

Y.-Y. Zhang et al. / Polyhedron 27 (2008) 2501–2505
2505
[23] D.A. Edwards, R.M. Harker, M.F. Mahon, K.C. Molloy, J. Mater. Chem. 9 (1999)
References
1771.
[24] J.L. Han, Y.Z. Shen, C.X. Li, Y.Z. Li, Y. Pan, Inorg. Chim. Acta 358 (2005)
[1] M. Dennehy, O.V. Quinzani, M. Jennings, J. Mol. Struct. 841 (2007) 110.
[2] I.G. Dance, Polyhedron 5 (1986) 1037.
[3] B. Krebs, G. Henkel, Angew. Chem., Int. Ed. Engl. 30 (1991) 769.
[4] C. Housecroft, Coord. Chem. Rev. 115 (1992) 141.
[5] R.H. Holm, P. Kennepohl, E.I. Solomon, Chem. Rev. 96 (1996) 2239.
[6] M.C. Hong, W.P. Su, R. Cao, W.J. Zhang, J.X. Lu, Inorg. Chem. 38 (1999) 600.
[7] F. Colombo, R. Annunziata, M. Benaglia, Tetrahedron Lett. 48 (2007) 2687.
[8] K. Ozawa, F. Iso, Y. Nakao, Z.X. Cheng, H. Fujii, M. Hase, H. Yamaguchi, J. Eur.
Ceram. Soc. 27 (2007) 2665.
[9] H. Schmidt, Y. Shen, M. Leschke, Th. Haase, K. Hohse-Hoeinghaus, H. Lang, J.
Organomet. Chem. 669 (2003) 25.
[10] W. Partenheimer, E.H. Johnson, Inorg. Chem. (11) (1972) 2840.
[11] W. Partenheimer, E.H. Johnson, Inorg. Chem. (12) (1973) 1274.
[12] H.K. Hofstee, J. Boersma, G.J.M. van der Kerk, J. Organomet. Chem. 120 (1976)
313.
[13] W.T. Miller, R.H. Sinder, R.J. Hummel, J. Am. Chem. Soc. 91 (1969) 6532.
[14] Y. Zheng, N.H. Dryden, J.J. Vittal, R.J. Puddephatt, Chem. Mater. 7 (1995) 1696.
[15] M. Wen, M. Munakata, Y.Z. Li, Y. Suenaga, T. Kuroda-Sowa, M. Maekawa, M.
Anahata, Polyhedron 26 (2007) 2455.
[16] J. Rickerby, J.H.G. Steinke, Chem. Rev. 102 (2002) 1525.
[17] H.K. Shin, K.M. Chi, J. Farkas, M.J. Hampden-Smith, T.T. Kodas, E.N. Duesler,
Inorg. Chem. 31 (1992) 424.
4417.
[25] D.A. Edwards, R.M. Harker, M.F. Mahon, K.C. Molloy, Inorg. Chim. Acta 328
(2002) 134.
[26] Bruker AXS Inc., SAINT, Area Detector Control and Data Integration and
Reduction Software, Madison, WI, USA, 1997.
[27] G.M. Sheldrick, SADABS, Program for Empirical Absorption Correction of Area
Detector Data, University of Gottingen, Germany, 1997.
[28] G.M. Sheldrick, SHELX-97, Programs for Crystal Structure Analysis (Release 97-
2), University of Gottingen, Germany, 1997.
[29] L. Zsolnai, G. Huttner, ORTEP, University of Heidelberg, Germany, 1994.
[30] L.J. Bellamy, The Infrared Spectra of Complexes Molecules, vol. 1, Chapman and
Hall, London, 1975.
[31] M.G. Miles, G. Doyle, R.P. Cooney, R.S. Tobis, Spectrochim. Acta A 25 (1960)
1515.
[32] R.J. Capwell, K.H. Rhee, K.S. Seshadri, Spectrochim. Acta A 24 (1968) 955.
[33] S.M. Chackalackal, F.E. Stafford, J. Am. Chem. Soc. 88 (1966) 4815.
[34] R. Bala, R.P. Sharma, A.D. Bond, J. Mol. Struct. 830 (2007) 198.
[35] C.Y. Panicker, H.T. Varghese, D. Philip, H.I.S. Nogueira, Spectrochim. Acta A 64
(2006) 744.
[36] D. Philip, A. Eapen, G. Aruldhas, J. Solid State Chem. 116 (1995) 217.
[37] D. Jamro, Y. Marechal, J. Phys. Chem. B. 109 (2005) 19664.
[38] R. Terroba, M.B. Hursthouse, M. Lagunab, A. Mendia, Polyhedron 18 (1999)
807.
[39] B.K. Teo, J.C. Calabrese, Inorg. Chem. 15 (1976) 2467.
[40] M.R. Churchill, K.L. Kalra, Inorg. Chem. 13 (1974) 1065.
[41] D.A. Edwards, M.F. Mahon, K.C. Molloy, V. Ogrodnik, Inorg. Chim. Acta 349
(2003) 37.
[18] A. Bailey, T.S. Corbitt, M.J. Hampden-Smith, E.N. Duesler, T.T. Kodas,
Polyhedron 12 (1993) 1785.
[19] D.A. Edwards, M. Longley, J. Inorg. Nucl. Chem. 40 (1978) 1599.
[20] G. Doyle, K.A. Erickson, D. Van Engen, Organometallics 4 (1985) 830.
[21] D. Gibson, B.F.G. Johnson, J. Lewis, J. Chem. Soc. A. (1970) 367.
[22] S.S. Monim, Z. Yuan, K. Griffiths, P.R. Norton, R.J. Puddephatt, J. Am. Chem. Soc.
117 (1995) 4030.
[42] M. Bardají, O. Crespo, A. Laguna, A.K. Fischer, Inorg. Chim. Acta 304 (2000) 7.