room temperature, with the appropriate lock solvent. Infrared
spectra were collected on a Bruker Vector 22 instrument as KBr
pellets at room temperature. Elemental analyses were performed
on a Perkin–Elmer 240 C elemental analyzer. Thermogravimetric
studies (TG) and differential scanning calorimetric (DSC) studies
were carried out with th◦e NETZSCH STA 409 PC/PG with a con-
stant heating rate of 10 C min-1 under N2 (30 cm3 min-1). Melting
points were observed in sealed capillaries and were uncorrected.
The MOCVD experiments were carried out in a vertical quartz
tube hot-wall MOCVD reactor, 60 mm in diameter. Heating
was achieved by a resistively heated tube oven (AICHUANG
Company). The temperature was set by a temperature control FP
93 (SHIMADEN Company) and calibrated with a thermocouple
type SR 3 (SHIMADEN Company) digital thermometer. The pre-
cursor container was heated with a heating band for evaporation of
the precursor. The precursor vapor was transported to the reactor
tube by N2 carrier gas. The carrier gas flow was regulated using
a D07-7B (SEVENSTAR Company) mass flow controller which
was connected to the apparatus by a section of flexible stainless
steel tubing. The pressure control system consisted of a cooling
trap and a FT-110 (KYKY Company) molecular pump unit. The
trap prevented the reactor effluents from entering the vacuum
pump. Scanning electron microscopy (SEM) images and Energy-
Dispersion X-ray Spectroscopy (EDX) analysis were carried out
by a Hitachi Model S-4800 with scanning electron microscope and
energy dispersive X-ray detector.
triphenylphosphine (0.3935 g, 1.50 mmol) instead. Yield: 0.55 g
(93%, based on [CH2(SO3)2Ag2]. M.p. (decomp.): 194 ◦C. Anal.
Calc. for C55H47O6Ag2P3S2: C, 56.14; H, 4.02. Found: C, 56.05; H,
3.94%. IR (KBr) data (cm-1): 3051 (m), 2925 (m), 2853 (m), 1478
(m), 1434 (vs), 1249 (vs), 1202 (vs), 1096 (m), 1064 (w), 1004 (m),
747 (s), 695 (vs), 577 (m), 509 (s). 1H NMR (CDCl3): d 4.1 (s, 2 H,
1
CH2-H), 7.2–7.4 (m, 45 H, Ph-H). 13C{ H} NMR (CDCl3): d 68.9
(CH2), 134.1 (JPC = 16.2 Hz, C6H5), 131.4 (JPC = 31.9 Hz, C6H5),
1
130.6 (C6H5), 129.0 (JPC = 9.7 Hz, C6H5). 31P{ H} NMR (CDCl3):
d 11.4.
Synthesis of [CH2(SO3)2Ag2·(PPh3)4] (2c)
Complex 2c as a white solid was synthesized in the same manner
as 2a. In this respect, [CH2(SO3)2Ag2] (0.2690 g, 0.69 mmol) was
reacted with triphenylphosphine (0.7239 g, 2.76 mmol). Yield:
0.93 g (94%, based on [CH2(SO3)2Ag2]). M.p. (decomp.):
202 ◦C. Anal. Calc. for C73H62O6Ag2P4S2: C, 60.93; H,
4.34. Found: C, 60.87; H, 4.56%. IR (KBr) data (cm-1):
3052 (m), 1480 (m), 1435 (vs), 1251 (s), 1204 (s), 1096
(m), 1026 (w), 1007 (m), 789 (m), 744 (s), 694 (vs),
1
578 (m), 505 (s). H NMR (CDCl3): d 3.9 (s, 2 H, CH2), 7.2–
1
7.4 (m, 60 H, Ph). 13C{ H} NMR (CDCl3): d 68.6 (CH2), 134.1
(JPC = 16.4 Hz, C6H5), 132.1 (JPC = 26.5 Hz, C6H5), 130.0 (C6H5),
1
128.8 (JPC = 9.4 Hz, C6H5). 31P{ H} NMR (CDCl3): d 8.0.
Synthesis of [CH2(SO3)2Ag2·(PPh3)5] (2d)
Synthesis of [CH2(SO3)2Ag2] (1)
Complex 2d as a white solid was prepared as described for 2a, only
using [CH2(SO3)2Ag2] (0.2690 g, 0.69 mmol) and triphenylphos-
phine (0.9049 g, 3.45 mmol) instead. Yield: 1.08 g (92%, based
on [CH2(SO3)2Ag2]). M.p. (decomp.): 208 ◦C. Anal. Calc. for
C91H77O6Ag2P5S2: C, 62.24; H, 4.56. Found: C, 62.15; H, 4.49%.
IR (KBr) data (cm-1): 3051 (m), 2926 (m), 1480 (m), 1434 (s), 1242
(s), 1200 (s), 1161 (m), 1095 (m), 1006 (m), 746 (s), 696 (vs), 578
Methanedisulphonic acid (4.58 g, 0.026 mol) dissolved in 30 mL
of H2O was added dropwise into a stirred suspended solution
of [Ag2CO3] (7.72 g, 0.028 mol) in 20 mL of H2O at 20 ◦C.
The clear solution 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 obtained after removing ◦the water in a rotary
evaporator and vacuum drying oven at 50 C. The product was
stored under nitrogen and kept in darkness. Yield: 8.52 g (84%,
based on Ag2CO3).
1
(m), 510 (s). H NMR (CDCl3): d 3.9 (s, 2 H, CH2), 7.2–7.4 (m,
1
75 H, Ph). 13C{ H} NMR (CDCl3): d 68.6 (CH2), 134.1 (JPC
=
16.8 Hz, C6H5), 132.8 (JPC = 22.2 Hz, C6H5), 129.9 (C6H5), 128.8
(JPC = 9.3 Hz, C6H5). 31P{ H} NMR (CDCl3): d 5.8.
1
Synthesis of [CH2(SO3)2Ag2·(PPh3)2] (2a)
Synthesis of [CH2(SO3)2Ag2·(PPh3)6] (2e)
Triphenylphosphine (0.2623 g, 1.00 mmol) dissolved in 20 mL of
CH2Cl2 was added dropwise into a stirred suspended solution of
[CH2(SO3)2Ag2] (0.1949 g, 0.50 mmol) in 20 mL of CH2Cl2 at 0 ◦C.
The clear solution was obtained by filtration thro◦ugh 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 vacuo using
an oil-pump. Yield: 0.42 g (92%, based on [CH2(SO3)2Ag2]. M.p.
(decomp.): 189 ◦C. Anal. Calc. for C37H32O6Ag2P2S2: C, 48.60;
H, 3.53. Found: C, 48.53; H, 3.44%. IR (KBr) data (cm-1): 3052
(m), 1479 (m), 1434 (vs), 1243 (s), 1202 (s), 1157 (w), 1095 (m),
Complex 2e as a white solid was prepared following the synthesis
of 2a. In this respect, triphenylphosphine (0.7869 g, 3.00 mmol)
was reacted with [CH2(SO3)2Ag2] (0.1949, 0.50 mmol). Yield: 0.92
g (94%, based on [CH2(SO3)2Ag2]). M.p. (decomp.): 215 ◦C. Anal.
Calc. for C109H92Ag2O6P6S2: C, 66.67; H, 4.72. Found: C, 66.58;
H, 4.62%. IR (KBr) data (cm-1): 3051 (m), 1479 (m), 1434 (vs),
1240 (s), 1201 (s), 1093 (m), 1026 (m), 1010 (m), 743 (s), 695 (vs),
1
579 (m), 514 (s). H NMR (CDCl3): d 3.9 (s, 2H, CH2), 7.2–7.4
1
(m, 90H, Ph). 13C{ H} NMR (CDCl3): d 68.9 (CH2), 133.9 (JPC
1
1008 (m), 791 (m), 745 (s), 694 (vs), 578 (m), 516 (s). H NMR
= 16.83 Hz, C6H5), 133.4 (JPC = 15.52 Hz, C6H5), 129.7 (C6H5),
1
(CDCl3): d 4.2 (s, 2H, CH2-H), 7.2–7.4 (m, 30H, Ph-H). 13C{ H}
1
128.7 (JPC = 8.73 Hz, C6H5). 31P{ H} NMR (CDCl3): d 5.0.
NMR (CDCl3): d 68.9 (CH2), 134.0 (JPC = 16.4 Hz, C6H5), 131.2
(JPC = 32.7 Hz, C6H5), 130.5 (C6H5), 129.0 (JPC = 10.0 Hz, C6H5).
Synthesis of {CH2(SO3)2Ag2·[P(OEt)3]2} (2f)
1
31P{ H} NMR (CDCl3): d 11.5.
Complex 2f was synthesized as described earlier (see synthesis of
2a). In this respect, [P(OEt)3] (1.8791 g, 11.32 mmol) was reacted
with [CH2(SO3)2Ag2] (2.2067 g, 5.66 mmol). After appropriate
work-up, complex 2f can be isolated as a white solid. Yield: 3.68 g
(90%, based on [CH2(SO3)2Ag2]. M.p. (decomp.): 47 ◦C. Anal.
Synthesis of [CH2(SO3)2Ag2·(PPh3)3] (2b)
Complex 2b as a white solid was obtained following the above
procedure, only using [CH2(SO3)2Ag2] (0.1949 g, 0.50 mmol) and
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The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 9250–9258 | 9251
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