2128 Jung et al.
Macromolecules, Vol. 38, No. 6, 2005
instruments SDT 2960 and DSC 2010 using heating rates of
10 °C/min in an atmosphere of nitrogen. Molecular weights
and molecular weight distributions, Mw/Mn, of polymer samples
were obtained on a Waters Associates gel permeation chro-
matograph (GPC) using 500, 104, 105, and 106 Å µ-Styragel
columns equipped with UV model 410 and refractive index
detectors. The system was calibrated with a series of narrow-
molecular-weight polystyrene standards in the molecular
weight range of ca. 103-106 g/mol using Polymer Standard
Service WINGPC 6 software for data processing. The samples
were eluted with HPLC-grade THF containing 0.1 wt% of
tetra-n-butylammonium bromide (n-Bu4NBr) with a flow rate
of 1.0 mL/min and column temperature of 30 °C. The injection
volume of samples was 0.05 mL of a 0.1% solution. UV/vis
absorption spectra of samples were obtained as solutions in
distilled THF or toluene using a Beckman DU Series 600
spectrophotometer operating in the range of 200-800 nm with
a scan speed of 1200 nm/min. The spectra were corrected for
the background absorbance of the solvent (THF or toluene).
TEM images were made using a JEOL 1200 EX microscope
operating at an accelerating voltage of 120 kV. Samples were
prepared by drop-casting a THF solution of the gold colloid
onto transparent carbon-coated copper grids (200 mesh) and
allowing to dry for 10 min. Digital TEM images were analyzed
to determine particle sizes using Image J software.
X-Ray Crystallography. Crystals for analyses of 3, cis-
[Ph(MeSCH2)PN]3 and 6, cis-[Ph(MeSO2CH2)PdN]3‚CHCl3,
were flat and colorless and grown from saturated ethyl acetate
and chloroform, respectively. The crystals were manipulated
under air during the mounting procedure. The X-ray data for
3 and 6 were collected on a Bruker P4 diffractometer using
the w scan technique at room temperature. The important
crystallographic data are summarized in Table 1. During the
data reduction, Lorentz and polarization corrections, as well
as a semiempirical absorption studies were applied. In the
structure of 6, there are two independent cyclic phosphazene
and two chloroform molecules. Among the solvent molecules,
one, C(72) through Cl(6), is disordered. Selected bond distances
and angles are listed in Table 2. Structures were refined
anisotropically on F2 (SHELXL97).28 Hydrogen atoms were
constrained with a riding model. Further details regarding the
crystal data and refinement, as well as full tables of bond
lengths and angles for each structure reported in this paper,
are presented in CIF format in the Supporting Information.
Preparation of cis-[Ph(MeSCH2)PN]3, 3. In a typical
procedure, 1.0 g (2.4 mmol) of cis-[Me(Ph)PN]3 was placed in
a two-neck, 50 mL round-bottom flask with a magnetic stir
bar, a nitrogen inlet adapter, and a rubber septum. Freshly
distilled THF (10 mL) and excess TMEDA (1.0 mL, 6.6 mmol)
were then added to the flask, and the mixture was cooled to
-78 °C. Then, n-BuLi (3.0 equiv) was added to the solution.
The white slurry was stirred for 4 h at that temperature, and
then 3.0 equiv of MeSSMe (0.76 mL) was added to the solution
at -78 °C. The mixture was stirred for 12 h before the volatiles
were removed under vacuum. The residue was dissolved in
20 mL of benzene and then filtered through a glass frit and a
layer of Celite. The volatiles were again removed under
vacuum, giving a pale yellow solid. This was dissolved with
dichloromethane and washed with KOH solution (1.5 M) to
remove MeSH. After removal of solvent with a rotary evapora-
tor, the residue was further dried at room temperature in a
vacuum overnight. Yield: 1.3 g, 97%.
{1H} (CDCl3): δ 18.6. IR (KBr, neat, cm-1): 3072 m, 3050 m,
2983 m, 2917 s, 2898 m, 2855 m, 1480 w, 1436 s, 1384 w, 1317
w, 1201 vs, 1157 vs, 1124 s, 1046 w, 1025 m, 997 m, 967 m,
859 m, 804 m, 791 m, 767 m, 742 m, 718 s, 696 s, 522 s, 473
m, 451 s, 423 s. Anal. Calcd for C24H30P3N3S3: C, 52.45; N,
7.65; H, 5.50. Found: C, 52.62; N, 7.68; H, 5.67. mp: 104 °C.
1
cis-[Ph3(MeSCH2)2MeP3N3], 4. H NMR (CDCl3): δ 1.87
(d, 3H, PCH3, JPh ) 14.3 Hz), 2.24 (s, 6H, PCH2SMe), 2.99 (d,
4 H, PCH2SMe, JPH ) 8.8 Hz), 7.19-7.24 (m, 3H, Ph), 7.25-
7.36 (m, 6 H, Ph), 7.63-7.69 (m, 2H, Ph), 7.76-7.82 (m, 4 H,
C6H5). 13C{1H} NMR (CDCl3): δ 17.9 (d, PCH2SMe, JPC ) 1.9
Hz,), 23.1 (d, PCH3, JPC ) 101.1), 38.4 (d, PCH2SCH3, JPC
)
99.1 Hz), 127.6 (d, Ph, JPC ) 13.6 Hz), 127.7 (d, Ph, JPC ) 10.7),
129.94 (s, Ph), 129.96 (d, Ph, JPC ) 11.7 Hz), 130.0 (d, Ph, JPC
) 10.7 Hz), 130.4 (s, Ph), 136.4 (d, Ph, JPC ) 128.3 Hz), 138.5
(d, Ph, JPC ) 124.4 Hz). 31P NMR{1H} (CDCl3): δ 18.3, 20.7.
IR (KBr, neat, cm-1): 3075 m, 3049 s, 3023 m, 3008 m, 2984
m, 2963 m, 2935 m, 2924 m, 2908 s, 2885 s, 1974 w, 1891 w,
1590 m, 1480 m, 1435 s, 1408 m, 1385 m, 1372 m, 1292 m,
1196 vs, 1158 vs, 1123 s, 1026 m, 999 m, 969 m, 914 m, 891
m, 861 s, 820 m, 795 m, 776 m, 748 m, 728 m, 716 s, 696 s,
668 m, 569 m, 522 s, 500 m, 470 m, 451 m, 435 m. Anal. Calcd
for C23H28P3N3S2: C, 54.86, N, 8.34, H, 5.60. Found: C, 55.02,
N, 8.32, H, 5.77. mp: 116-117 °C.
Preparation of cis-[Ph(PhSCH2)PN]3, 5. This compound
was prepared by a procedure analogous to that used for the
preparation of 3 using TMEDA to assist in the deprotonation.
The compound 5 was purified and isolated by column chro-
matography [silica gel 60 Å columns (25 mm × 250 mm);
elution with 1:1 ethyl acetate/hexane] as a pale yellow colored
1
solid. Yield 5: 43%, Rf ) 0.37. H NMR (CDCl3): δ 3.60 (d, 6
H, PCH2SPh, JPH ) 10.2 Hz), 7.15 (t, 3H, Ph, JHH ) 7.8 Hz),
7.25 (t, 6H, Ph, JHH ) 7.6 Hz), 7.35-7.41 (m, 15 H, Ph), 7.96-
8.02 (m, 6 H, Ph). 13C NMR{1H} (CDCl3): δ 38.7 (d, PCH2-
SPh, JPC ) 95.2 Hz), 125.7 (s, Ph), 127.8 (d, Ph, JPC ) 12.9
Hz), 128.58 (s, Ph), 128.62 (s, Ph), 130.3 (d, Ph, JPC ) 10.7
Hz), 130.8 (s, Ph), 135.8 (d, Ph, JPC ) 132.2 Hz), 137.1 (d, Ph,
JPC ) 5.8 Hz). 31P NMR{1H} (CDCl3): δ 17.6. IR (KBr, neat,
cm-1): 3073 s, 3055 s, 3018 m, 2989 w, 2904 m, 1960 m, 1891
m, 1581 s, 1479 s, 1437 s, 1383 m, 1197 vs, 1156 vs, 1124 s,
1087 m, 1025 m, 998 m, 908 m, 870 m, 788 m, 736 m, 690 s,
569 s. Anal. Calcd for C39H36P3N3S3: C, 63.66, N, 5.71, H, 4.93.
Found: C, 63.65, N, 5.40, H, 4.86. mp: 77 °C.
Preparation of cis-{Ph[MeS(O)2CH2]PN}3, 6. Compound
3 (0.59 g, 1.1 mmol) and 20 mL of chloroform were placed in
a 50 mL two-neck round-bottom reaction flask, and the
solution was cooled to 0 °C. Then, excess MCPBA was added.
The mixture was stirred at room temperature for 30 min, and
then distilled water (30 mL) was added to reaction mixture.
The organic layer was separated, washed with distilled water
(30 mL) twice, and dried over sodium sulfate. The volatiles
were removed under reduced pressure to give a white powder
(0.50 g, 69% yield) as a spectroscopically pure product. Re-
crystallization of 5 from dichloromethane afforded colorless
crystals. 1H NMR (CDCl3): δ 3.069 (s, 9H, PCH2S(O)2Me), 4.51
(d, 6 H, PCH2S(O)2Me, JHP ) 12.1 Hz), 7.34-7.44 (m, 9 H, Ph),
7.82-7.87 (m, 6 H, Ph). 13C NMR{1H} (CDCl3): δ 43.6 (s,
PCH2S(O)2Me), 58.9 (d, PCH2S(O)2CH3, JPC ) 84.6 Hz), 128.1
(d, Ph, JPC ) 14.6 Hz), 130.0 (d, Ph, JPC ) 11.7 Hz), 131.7 (s,
Ph), 134.4 (d, Ph, JPC ) 142.9 Hz). 31P NMR{1H} (CDCl3): δ
9.2. IR (KBr, pellet, cm-1): 3059 m, 3011 m, 2960 s, 2912 s,
1984 w, 1904 w, 1774 s, 1708 s, 1590 m, 1574 m, 1481 m, 1437
s, 1360 w, 1303 vs, 1207 vs, 1176 s, 1145 vs, 1124 s, 1093 s,
1027 m, 997 m, 961 s, 890 m, 876 m, 837 m, 809 s, 767 s, 748
s, 693 s, 547 m, 512 m, 501 s, 446 s. Anal. Calcd for
C24H30N3O6P3S3: C, 44.65, N, 6.51, H, 4.68. Found: C, 44.81,
N, 6.50, H, 4.74. mp: 259 °C.
When the reaction was carried out without TMEDA, a
40:60 mixture of di- (4) and trisubstituted (3) thioether
1
derivatives was obtained, as determined by H and 31P NMR
spectroscopy. The two compounds were purified and separated
by column chromatography [silica gel 60 Å columns (25 mm
× 250 mm) and elution with 1:1 ethyl acetate/hexane]. Yield:
3, 28%, Rf ) 0.56; 4, 16%, Rf ) 0.71.
Preparation of cis-(Ph(PhS(O)2CH2)PdN)3, 7. This com-
pound was prepared from 0.60 g of 5 by a procedure analogous
to that used for the preparation of 6. Compound 7 was isolated
in 64% as a pale yellow colored white powder by solvent
removal and further purified by column chromatography [silica
gel 60 Å columns (25 mm × 250 mm); elution with 5:5:2 ethyl
cis-[Ph(MeSCH2)PN]3, 3. 1H NMR (CDCl3): δ 2.18 (s, 9H,
PCH2SMe), 3.02 (d, 6 H, PCH2SMe, JPH ) 9.3 Hz), 7.27-7.32
(m, 9 H, Ph), 7.80-7.83 (m, 6 H, Ph). 13C NMR{1H} (CDCl3):
δ 17.9 (d, PCH2SMe, JPC ) 1.9 Hz,), 38.4 (d, PCH2SMe, JPC
)
1
98.5 Hz), 127.5 (d, Ph, JPC ) 13.5 Hz), 130.2 (d, Ph, JPC ) 11
acetate/hexane/methanol]. 7, Rf ) 0.53. H NMR (CDCl3): δ
Hz), 130.4 (s, Ph), 136.1 (d, Ph, JPC ) 128.5 Hz). 31P NMR-
4.01 (d, 6 H, PCH2S(O)2Ph, JPH ) 12.5 Hz), 7.3-7.9 (m, 9 H,