C. Di Nicola et al. / Inorganica Chimica Acta 360 (2007) 2935–2943
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MePh2P (0.200 g, 1 mmol). After the addition, the solution
was stirred for 24 h at room temperature. A colorless pre-
cipitate was formed which was filtered off and washed with
ethanol (3 · 5 mL). Recrystallization from ethanol gave
complex 6 as a microcrystalline solid in 81% yield. M.p.:
106–108 ꢁC. IR data (Nujol, cmꢀ1): 3060br (CH), 1481s
(CC), 985 (CS), 694s, 617w, 604w, 595w, 562m, 508s,
dppe (0.400 g, 1 mmol). After the addition, the solution
was stirred for 24 h at room temperature. A colorless pre-
cipitate was formed which was filtered off and washed
with ethanol (3 · 5 mL). Recrystallization from ethanol
gave complex 9 as a microcrystalline solid in 82% yield.
M.p.: 238–241 ꢁC. IR data (Nujol, cmꢀ1): 1468w,
1455m, 1431m, 1404m, 1374m, 1354s, 1301s, 1261m,
1207m, 1131m, 1094s, 1064s, 1024s, 984s, 907m, 837m,
777s, 747m, 723m, 693m, 563s, 511m, 476m, 417s, 347s,
1
477w, 465m, 430m, 417w, 393w, 361w, 347w, 321w. H
NMR (CDCl3, 293 K): 1.32 (t, 6H, CH3dtc), 1.94 (d, 3H,
1
CH3PMePh ), 3.97 (q, 4H, CH2dtc), 7.38–7.62 (m, 10H,
280s, 246s, 227. H NMR (CDCl3, 293 K): 1.35 (t, 6H,
2
CHPMePh ). 31P{1H} NMR (CDCl3, 293 K):
d
ꢀ5.5
CH3dtc), 2.36 (m, 4H, CH2dppe), 4.06 (q, 4H, CH2dtc),
7.3–7.7 (m, 20H, CH2dppe). 31P{1H} NMR (CDCl3,
293 K): d ꢀ1.5br. Kmol (CH2Cl2, conc. = 1.03 · 10ꢀ3 M):
0.6 Xꢀ1 cm2 molꢀ1. Anal. Calc. for C31H34AgNP2S2: C,
56.88; H, 5.24; N, 2.14; S, 9.80. Found: C, 57.12; H,
5.11; N, 2.15; S, 9.63%.
2
(s).31P{1H} NMR (CDCl3, 223 K): d ꢀ5.9 (s br). Kmol
(CH2Cl2, conc. = 1.00 · 10ꢀ3 M): 0.2 Xꢀ1 cm2 molꢀ1
Anal. Calc. for C18H23AgNPS2: C, 47.38; H, 5.08; N,
.
3.07; S, 14.05. Found: C, 46.98; H, 5.30; N, 3.36; S, 14.25%.
2.2.7. Synthesis of [Ag(dtc)(PMePh2)2] (7)
Silver(I) diethyldithiocarbamate (Ag(dtc)) (0.254 g,
1 mmol) was added to an ethanol solution (30 mL) of
MePh2P (0.500 g, 2.5 mmol). After the addition, the solu-
tion was stirred for 24 h at room temperature. A colorless
precipitate was formed which was filtered off and washed
with ethanol (3 · 5 mL). Recrystallization from ethanol
gave complex 7 as a microcrystalline solid in 87% yield.
M.p.: 119–122 ꢁC. IR data (Nujol, cmꢀ1): 3060br (CH),
1481s (CC), 985 (CS), 694s, 616w, 605w, 564w, 506s,
2.2.10. Synthesis of [Ag(dtc)(dppp)] (10)
Silver(I) diethyldithiocarbamate (Ag(dtc)) (0.254 g,
1 mmol) was added to an ethanol solution (30 mL) of
dppp (0.412 g, 1 mmol). After the addition, the solution
was stirred for 24 h at room temperature. The colorless
precipitate formed was filtered off and washed with etha-
nol (3 · 5 mL). Recrystallization from ethanol gave com-
plex 10 as a microcrystalline solid in 50% yield. M.p.:
163–164 ꢁC. IR data (Nujol, cmꢀ1): 992w (CS), 518m,
509s, 496m, 473m, 432m, 385w, 321w, 296w, 24w. 1H
NMR (CDCl3, 293 K): 1.30 (t, 6H, CH3dtc), 1.78m,
2.30s (6H, CH2dppp), 4.01 (q, 4H, CH2dtc), 7.1–7.5 (m,
1
477m, 466m, 432m, 412w, 395w, 545w. H NMR (CDCl3,
293 K): 1.24 (t, 6H, CH3dtc), 1.74 (d, 6H, CH3PMePh ), 3.93
2
(q, 4H, CH2dtc), 7.22–7.50 (m, 20H, CHPMePh ). 31P{1H}
2
NMR (CDCl3, 293 K): d ꢀ12.8 (s br). 31P{1H} NMR
20H, CH2dppm). 31P{1H} NMR (CDCl3, 293 K):
d
(CDCl3, 223 K): d ꢀ11.6 (s br). Kmol (CH2Cl2, conc.
ꢀ3.1s. 31P{1H} NMR (CDCl3, 223 K): d ꢀ3.6 (dd,
= 1.00 · 10ꢀ3 M): 0.3 Xꢀ1 cm2 molꢀ1
. Anal. Calc. for
1J(107Ag–31P): 346 Hz; dd, 1J(109Ag–31P): 398 Hz). Kmol
C31H36AgNP2S2: C, 56.71; H, 5.53; N, 2.13; S, 9.77.
Found: C, 56.45; H, 5.82; N, 2.27; S, 10.02%.
(CH2Cl2, conc. = 1.03 · 10ꢀ3 M): 0.4 Xꢀ1 cm2 molꢀ1
.
Anal. Calc. for C32H36AgNP2S2: C, 57.49; H, 5.43; N,
2.09; S, 9.59. Found: C, 57.30; H, 5.71; N, 2.13; S,
9.41%.
2.2.8. Synthesis of [Ag(dtc)(dppm)] (8)
Silver(I) diethyldithiocarbamate (Ag(dtc)) (0.254 g,
1 mmol) was added to an ethanol solution (30 mL) of
dppm (0.384 g, 1 mmol). After the addition, the solution
was stirred for 24 h at room temperature. A colorless pre-
cipitate formed which was filtered off and washed with eth-
anol (3 · 5 mL). Recrystallization from ethanol gave
complex 8 as a microcrystalline solid in 80% yield. M.p.:
95–98 ꢁC dec. IR data (Nujol, cmꢀ1): 3060w (CH), 997w,
987m (CS), 5151s, 505s, 471s, 444w, 430w, 409w, 385w,
351w, 279w, 248w. 1H NMR (CDCl3, 293 K): 1.21 (t,
6H, CH3dtc), 3.10 (br, 2H, CH2dppm), 3.92 (q, 4H, CH2dtc),
7.1–7.5 (m, 20H, CH2dppm). 31P{1H} NMR (CDCl3,
293 K): d ꢀ7.9 br. 31P{1H} NMR (CDCl3, 223 K): d
ꢀ5.1 (br, 1J(Ag–31P): 259 Hz). Kmol (CH2Cl2, con-
c. = 1.03 · 10ꢀ3 M): 1.3 Xꢀ1 cm2 molꢀ1. Anal. Calc. for
C30H32AgNP2S2: C, 56.25; H, 5.04; N, 2.19; S, 10.01.
Found: C, 55.98; H, 5.02; N, 2.13; S, 9.85%.
2.2.11. Synthesis of [Ag(dtc)(dppb)] (11)
Silver(I) diethyldithiocarbamate (Ag(dtc)) (0.254 g,
1 mmol) was added to an ethanol solution (30 mL) of dppb
(0.425 g, 1 mmol). After the addition, the solution was stir-
red during 24 h at room temperature. A colorless precipi-
tate was formed which was filtered off and washed with
ethanol (3 · 5 mL). Recrystallization from ethanol gave
complex 11 as a microcrystalline solid in 92% yield.
M.p. > 200 ꢁC. IR data (Nujol, cmꢀ1): 3060sh, 1569w,
1558w, 1420s, 1406m, 1352m, 992w, 617w, 599w, 570w,
518m, 508s, 488s, 455w, 440w, 414w, 398w, 364w, 315w,
301w, 279w, 247w. 1H NMR (CDCl3, 293 K): 1.29 (t,
6H, CH3dtc), 1.60 br, 2.05 br (8H, CH2dppb), 4.01 (q, 4H,
CH2dtc), 7.2–7.5 (m, 20H, CH2dppb). 31P{1H} NMR
(CDCl3, 293 K): d ꢀ2.2br. 31P{1H} NMR (CDCl3,
1
1
293 K): d ꢀ2.6 (dd, J(109Ag–31P): 396 Hz; J(107Ag–31P):
346 Hz).
Kmol
(CH2Cl2,
conc. = 1.03 · 10ꢀ3 M):
2.2.9. Synthesis of [Ag(dtc)(dppe)] (9)
Silver(I) diethyldithiocarbamate (Ag(dtc)) (0.254 g,
1 mmol) was added to an ethanol solution (30 mL) of
0.4 Xꢀ1 cm2 molꢀ1. Anal. Calc. for C33H38AgNP2S2: C,
58.07; H, 5.61; N, 2.05; S, 9.39. Found: C, 58.02; H, 5.68;
N, 2.00; S, 9.53%.