K.-H. Yih, G.-H. Lee / Journal of Organometallic Chemistry 691 (2006) 3997–4005
4003
3. Experimental
vacuum and n-hexane (10 ml) was added to initiate precip-
itation. The yellow-orange solids 4 were formed which were
isolated by filtration (G4), washed with n-hexane
(2 · 10 ml) and subsequently dried under vacuum yielding
[Pt(PPh3)2(g2-SCNMe2)][PF6], 4 (0.88 g, 92%). Further
purification was accomplished by recrystallization from
1/10 CH2Cl2/n-hexane. Spectroscopic data of 4 are as fol-
lows. IR (KBr, cmꢀ1) m(CN) 1476(m), 1432(m); m(PF6)
837(vs). 1H NMR (500 MHz, CDCl3, 298 K): d 2.35,
3.57 (s, 6H, NCH3), 7.24–7.46 (m, 35H, Ph). 31P{1H}
NMR (202 MHz, CDCl3, 298 K): d 16.3, 22.7 (d, PPh3,
2JP–P = 11, JPt–P = 1525, JPt–P = 2097), ꢀ143.9 (sep, PF6,
JP–F = 713). 13C{1H} NMR (125 MHz, CDCl3, 298 K): d
3.1. Materials
All manipulations were performed under nitrogen using
vacuum-line, drybox, and standard Schlenk techniques.
NMR spectra were recorded on a Bruker AM-500 WB
FT-NMR spectrometer and are reported in units of d
(ppm) with residual protons in the solvent as an internal
standard (CDCl3, d 7.24). IR spectra were measured on a
Nicolate Avator-320 instrument and were referenced to a
polystyrene standard, using cells equipped with calcium
fluoride windows. Mass spectra were recorded on a JEOL
SX-102A spectrometer. Solvents were dried and deoxygen-
ated by refluxing over the appropriate reagents before use.
n-Hexane, diethyl ether, THF and benzene were distilled
from sodium-benzophenone. Acetonitrile and dichloro-
methane were distilled from calcium hydride. Methanol
was distilled from magnesium. All other solvents and
reagents were of reagent grade and were used as received.
Elemental analyses and X-ray diffraction studies were
carried out at the Regional Center of Analytical Instru-
mentation located at the National Taiwan University.
PtCl2 Æ xH2O was purchased from Strem Chemical,
EtOCS2K, dppa, and NH4PF6 were purchased from
Merck.
4
46.3, 54.0 (d, NCH3, JP–C = 6.19), 129.3–134.8 (m, C of
2
Ph), 216.2 (d, CS, JP–C = 6.2). MS (FAB, NBA, m/z):
807.3 [M+ ꢀ PF6], 719.3 [M+ ꢀ PF6 ꢀ CSNMe2], 545.1
[M+ ꢀ PF6 ꢀ PPh3]. Anal. Calc. for C39H36F6NP3SPt: C,
49.16; H, 3.81; N, 1.47. Found: C, 49.28; H, 4.06; N,
1.51%.
3.4. [{g2-Bis(triphenylphosphino)amine}(g1-N,N-
dimethylthiocarbamoyl)(triphenylphosphine) platinum(II)]
[chloride] (5)
CH2Cl2 (40 mL) was added to a flask (100 mL) contain-
ing [Pt(PPh3)2(g1-SCNMe2)(Cl)] (1) (0.843 g, 1.0 mmol)
and dppa (0.384 g, 1.0 mmol) and the solution was stirred
at room temperature. After stirring 1 h, MeOH (10 mL)
was added to the solution and the brown solids were
formed which were isolated by filtration (G4), washed with
n-hexane (2 · 10 ml) and subsequently dried under vacuum
3.2. Bis-[(chlorotriphenylphosphine)][l-bis-{g2-N,N-
dimethylthiocarbamoyl}] platinum(II) (2)
CHCl3 (20 ml) was added to a flask (100 ml) containing
[Pt(PPh3)2(g1-SCNMe2)(Cl)] (1) [13b] (0.843 g, 1.0 mmol).
The solution was refluxed for 8 h then diethyl ether
(30 ml) was added to the solution and a yellow precipitate
was formed. The precipitate was collected by filtration (G4)
washed with n-hexane (2 · 10 ml) and then dried in vacuo
yielding 0.54 g (93%) of 2. Spectroscopy for2: IR (KBr,
yielding
0.85 g
(88%)
of
[Pt(g1-SCNMe2)(g2-
dppa)(PPh3)][Cl] (5). IR (KBr, cmꢀ1) m(CN) 1470(m),
1429(m). 1H NMR (500 MHz, CDCl3 298 K): d 2.58,
2.81 (s, 6H, NCH3), 7.14–7.76 (m, 30H, Ph). 31P{1H}
NMR (202 MHz, CDCl3, 298 K): d 13.3 (m, dppa,
JPt–P = 1417), 16.1 (m, PPh3, JPt–P = 729). 13C{1H} NMR
(125 MHz, CDCl3, 298 K): d 40.3, 45.7 (d, NCH3,
4JP–C = 4.53), 128.2–137.2 (m, C of Ph), 225.5 (s, CS).
MS (FAB, NBA, m/z): 930.4 [M+ ꢀ Cl], 842.4
[M+ ꢀ Cl ꢀ SCNMe2]. Anal. Calc. for C45H42ClN2P3SPt:
C, 55.93; H, 4.38; N, 2.90. Found: C, 56.04; H, 4.46; N,
3.08%.
cmꢀ1
)
m(CN) 1481(m), 1435(m). 31P{1H} NMR
(202 MHz, CDCl3, 298 K): d 9.51 (s, PPh3, JPt–P
=
1826 Hz). 1H NMR (500 MHz, CDCl3, 298 K): d 2.48,
3.27 (s, 6H, NCH3), 7.28–7.80 (m, 30H, Ph). 13C{1H}
NMR (125 MHz, CDCl3, 298 K): d 39.8, 48.7 (s, NCH3),
127.8–135.3 (m, C of Ph), 213.6 (s, CS). MS (FAB, NBA,
m/z): 1125 [M+ ꢀ Cl]. Anal. Calc. for C42H42Cl2N2P2S2Pt2:
C, 43.41; H, 3.64; N, 2.41. Found: C, 43.28; H, 3.58; N,
2.20%.
3.5. [(g2-Ethyldithiocarbonate)(g1-N,N-dimethylthio-
carbamoyl)(triphenylphosphine) platinum(II)] (6)
3.3. [(Bis(triphenylphosphine) (g2-N,N-dimethylthio-
carbamoyl) platinum(II)) [hexafluorophosphate] (4)
IR (KBr, cmꢀ1) m(CN) 1475(m), 1437(m). 1H NMR
(500 MHz, CDCl3 298 K): d 1.35 (t, 3H, OCH2CH3,
JH–H = 4.7), 2.95, 3.22 (s, 6H, 2NCH3), 4.07 (q, 2H,
OCH2, JH–H = 4.7), 7.17–7.75 (m, 15H, Ph). 31P{1H}
Acetone (20 ml) was added to a flask (100 ml) contain-
ing NH4PF6 (0.163 g, 1.0 mmol) and [Pt(PPh3)2(g1-
SCNMe2)(Cl)] (1) (0.843 g, 1.0 mmol). The solution was
stirred for 20 min at room temperature. The solvent was
then removed under vacuum. The remaining solid was dis-
solved in 10 ml of CH2Cl2 and the solution was filtered to
remove excess NH4Cl. The solution is concentrated under
NMR (202 MHz, CDCl3 298 K):
d 11.2 (s, PPh3,
JPt–P = 2128). 13C{1H} NMR (125 MHz, CDCl3 298 K):
d 31.5 (s, OCH2CH3), 39.8, 48.9 (s, NCH3, JPt–C = 17.4,
47.1), 68.7 (s, OCH2), 128.2–134.4 (m, C of Ph), 194.4
(s, S2CO), 233.8 (s, NCSEt). MS (FAB, NBA, m/z): 667
[M+].
Yih, Kuang-Hway
