MgSO4 . The dried organic fraction was then concentrated
under reduced pressure and pass through a column of acti-
vated basic alumina (50–200 mm) using CH2Cl2–petroleum
6.8 Hz, 2H, NCH2–), 7.20–7.26 (m, 6H, aromatic Hs), 7.30–
7.40 (m, 6H, aromatic Hs), 7.92 (d, JHH ¼ 1.7 Hz, 2H, Hs at
4-position of carbazole); 31P{1H} NMR (CDCl3 , 298 K, 162
MHz): d 11.5 (JPt–P ¼ 2374 Hz); IR (KBr disk, n/cmꢂ1):
ꢀ
ether (bp 40–60 C) (1:1, v/v) as eluent. Subsequent recrystal-
lization from CH2Cl2–n-hexane gave 1 as pale yellow crystals.
+
=
2096s n(C C); positive FAB-MS: 1525 [M] , 1407 [M ꢂ PEt ];
=
anal. calcd. for 4: C, 55.1%; H, 6.62%; N, 0.92%; found: C,
3
1
Yield: 69%. H NMR (CDCl3 , 298 K, 400 MHz): d 0.92 (t,
JHH ¼ 6.8 Hz, 3H, –NCH2CH2CH2CH3), 1.20–1.30 (m, 38H,
–PCH2CH3 and –NCH2CH2CH2–), 1.81 (quintet, JHH ¼ 6.8
Hz, 2H, –NCH2CH2–), 2.05–2.15 (m, 24H, –CH2P), 4.22 (t,
JHH ¼ 6.8 Hz, 2H, NCH2–), 7.21 (d, JHH ¼ 8.6 Hz, 2H, Hs
at 1-position of carbazole), 7.34 (dd, JHH ¼ 8.6 Hz/1.7 Hz,
2H, Hs at 2-position of carbazole), 7.92 (d, JHH ¼ 1.7 Hz,
2H, Hs at 4-position of carbazole); 31P{1H} NMR (CDCl3 ,
55.0%; H, 6.63%; N, 0.92%.
=
n
=
=
=
2
3,6-{HC CC H C CPt(PEt ) C C} -9- BuCarb (5). The
=
=
6
4
3
2
trimethylsilyl protecting groups in 4 were removed by the stan-
dard procedure13 to give 5. Yield: 91%. 1H NMR (CDCl3 , 298
K, 400 MHz): d 0.92 (t, JHH ¼ 6.8 Hz, 3H, –NCH2CH2-
CH2CH3), 1.20–1.30 (m, 38H, –PCH2CH3 and –NCH2CH2-
CH2CH3), 1.81 (quintet, JHH ¼ 6.8 Hz, 2H, –NCH2CH2-
=
=
298 K, 162 MHz): d 15.1 (JPt–P ¼ 2401 Hz); IR (KBr disk,
CH CH ), 2.05–2.15 (m, 24H, –CH P), 3.09 (s, –C CH),
2
3
2
+
n/cmꢂ1): 2117s n(C C); positive FAB-MS: 1202 [M] , 1084
4.22 (t, JHH ¼ 6.8 Hz, 2H, NCH2–), 7.20–7.26 (m, 6H, aro-
matic Hs), 7.30–7.40 (m, 6H, aromatic Hs), 7.92 (d, JHH ¼ 1.7
1.7 Hz, 2H, Hs at 4-position of carbazole); 31P{1H} NMR
(CDCl3 , 298 K, 162 MHz): d 11.5 (JPt–P ¼ 2375 Hz); IR
=
=
[M ꢂ PEt3]+; anal. calcd. for 1: C, 43.9%; H, 6.24%; N,
1.16%; found: C, 44.0%; H, 6.23%; N, 1.16%.
t
[Pt( Bu trpy)(C CC H C CH)]OTf (2). 1,4-Diethynylben-
(KBr disk, n/cmꢂ1): 2096s n(C C); positive FAB-MS: 1381
=
=
=
4
=
=
=
3
6
zene (42 mg, 0.334 mmol), [Pt(tBu3trpy)(MeCN)](OTf)2 (312
mg, 0.334 mmol) and sodium hydroxide (0.2 g) in methanol
(35 ml) were heated to reflux overnight. The solvent of the
red reaction mixture was removed under reduced pressure.
The residue was dissolved in CH2Cl2 , filtered and chomato-
graphed on silica gel (60–230 mesh) using CH2Cl2–acetone as
eluent. Recrystallization from acetone–n-hexane gave 2 as
orange crystals. Yield: 42%. 1H NMR (CDCl3 , 298 K, 400
MHz): d 1.50 (s, 18H, tBu), 1.59 (s, 9H, tBu), 7.42 (dd, JHH ¼ 6
6 Hz/2 Hz, 4H, –C6H4–), 7.62 (dd, JHH ¼ 6 Hz/2 Hz, 2H,
trpy), 8.38, (d, JHH ¼ 2 Hz, 2H, trpy), 8.45 (s, 2H, trpy),
[M]+, 1263 [M ꢂ PEt3]; anal. calcd. for 5: C, 55.6%; H,
6.15%; N, 1.01%; found: C, 55.5%; H, 6.16%; N, 1.01%.
t
=
=
=
=
=
2
[3,6-{Pt( Bu trpy)(C CC H C C)Pt(PEt ) C C} -
=
3
6
4
3
2
9-nBuCarb](OTf)2 (3). 5 (100 mg, 0.066 mmol), [Pt(tBu3-
trpy)(MeCN)](OTf)2 (153 mg, 0.164 mmol) and sodium hydro-
xide (0.5 g) in methanol/THF (1:1, v/v, 35 ml) was heated to
reflux overnight. The solvent of the red reaction mixture was
removed under reduced pressure. The residue was dissolved
in CH2Cl2 , filtered and chomatographed on activated basic
alumina (50–200 mm) using CH2Cl2–acetone as eluent. Recrys-
tallization from acetone–n-hexane gave 3 as a deep red solid.
Yield: 29%.
9.10 (d, JHH ¼ 6 Hz, 4H, trpy); IR (KBr disk, n/cmꢂ1):
+
=
2112s n(C C); positive ESI-MS: 720 [M ꢂ OTf] , anal. calcd.
=
for 2: C, 52.4%; H, 4.60%; N, 4.83%; found: C, 52.3%; H,
4.61%; N, 4.82%.
X-Ray crystallography
A single crystal of complex 1 of dimensions 0.3 ꢃ 0.2 ꢃ 0.1 mm
mounted in a glass capilliary with mother liquor was used for
data collection at 28 ꢀC on a MAR diffractometer with a 300
mm image plate detector using graphite monochromatized
t
n
=
=
=
=
3 2
[3,6-{Pt( Bu trpy)(C CC H C C)Pt(PEt ) C C} -9- Bu-
=
=
3
6
4
2
Carb](OTf)2 (3) via the convergent route. 1 (78 mg, 0.065 mmol)
and 2 (100 mg, 0.142 mmol) were dissolved in THF (15 ml)
containing copper(I) chloride (0.1 mg, 0.001 mmol) and
triethylamine (1 ml). The mixture was stirred at room tempera-
ture overnight and the workup was similar to that of 2 using
activated basic alumina (50–200 mm) for column chromato-
graphy. Subsequent recrystallization from acetone-diethyl
ether gave analytically pure samples of 3 as a deep red
solid. Yield: 15%. 1H NMR (CDCl3 , 298 K, 400 MHz): d
0.92 (t, JHH ¼ 6.8 Hz, 3H, –NCH2CH2CH2CH3), 1.20–1.30
(m, 38H, –PCH2CH3 and –NCH2CH2CH2CH3), 1.50 (s,
˚
Mo-Ka radiation (l ¼ 0.71073 A). The images were inter-
preted and intensities integrated using the program DENZO.14
The structure was solved by direct methods employing the
SHELXS-97 program.15 Positions of other non-hydrogen
atoms were found after successful refinement by full-matrix
least-squares using the program SHELXL-97.16 The ethyl
groups of the PEt3 ligands have relatively high thermal para-
meters and a disorder model was not introduced. One crystal-
lographic asymmetric unit consists of one formula unit,
including one ethanol solvent molecule. In the final stage of
least-squares refinement, atoms of the ethyl groups and the
ethanol solvent molecule were refined isotropically, and other
non-hydrogen atoms anisotropically. The positions of hydro-
gen atoms were calculated based on a riding mode with ther-
mal parameters equal to 1.2 times those of the associated C
atoms, and participated in the calculation of final R indices.
A single crystal of complex 2 of dimensions 0.6 ꢃ 0.2 ꢃ 0.1
mm mounted in a glass capillary was used for data collection
at 28 ꢀC on a MAR diffractometer with a 300 mm image plate
detector using graphite monochromatized Mo-Ka radiation
36H,tBu), 1.59 (s, 18H, Bu), 1.81 (quintet, JHH ¼ 6.8 Hz,
t
2H, –NCH2CH2CH2CH3), 2.05–2.15 (m, 24H, –CH2P), 4.22
(t, JHH ¼ 6.8 Hz, 2H, NCH2–), 7.20–7.26 (m, 6H, aromatic
Hs), 7.35–7.40 (m, 6H, aromatic Hs), 7.62 (dd, JHH ¼ 6 Hz/
2 Hz, 2H, trpy), 7.92 (d, JHH ¼ 1.7 Hz, 2H, Hs at 4-position
of carbazole), 8.39, (d, JHH ¼ 2 Hz, 4H, trpy), 8.45 (s, 4H,
trpy), 9.17 (d, JHH ¼ 6 Hz, 4H, trpy); 31P{1H} NMR (CDCl3 ,
298 K, 162 MHz): d 11.4 (JPt–P ¼ 2374 Hz); IR (KBr disk,
n/cmꢂ1): 2094s n(C C); positive ESI-MS: 1286 [M ꢂ 2OTf]
2+
,
=
=
anal. calcd. for 3: C, 50.2%; H, 5.33%; N, 3.42%; found: C,
50.1%; H, 5.34%; N, 3.43%.
˚
(l ¼ 0.71073 A). The images were interpreted and intensities
t
n
integrated using the program DENZO.14 The structure was
solved by direct methods employing the SIR-97 program.17
Pt and many non-hydrogen atoms were located according to
direct methods and successive least-squares Fourier cycles.
Positions of other non-hydrogen atoms were found after
successful refinement by full-matrix least-squares using the
program SHELXL-97.16 One water, one acetone and half of
n-hexane solvent molecules were also located. For convergence
of least-square refinements, restraints were applied to the
=
=
=
=
=
=
3 2
[3,6-{Pt( Bu trpy)(C CC H C C)Pt(PEt ) C C} -9- Bu-
3
6
4
2
=
Carb](OTf)2 (3) via the divergent route. 3,6-{TMSC CC -
6
H C CPt(PEt ) C C} -9- BuCarb (4). 4 was synthesized
=
n
=
=
=
=
4
3
2
2
according to a procedure similar to the convergent synthesis
of 3, except that 1-ethynyl-4-trimethlysilylethynylbenzene was
used in place of 2 and CH2Cl2 was used as the eluent instead
of CH2Cl2–acetone. Yield: 78%. 1H NMR (CDCl3 , 298 K,
400 MHz): d 0.24 (s, 18H, TMS), 0.92 (t, JHH ¼ 6.8 Hz, 3H,
–NCH2CH2CH2CH3), 1.20–1.30 (m, 38H, –PCH2CH3 and –NC-
H2CH2CH2CH3), 1.81 (quintet, JHH ¼ 6.8 Hz, 2H, –NCH2-
ꢂ
CF3SO3 anion, assuming similar C–F, S–O, Sꢁ ꢁ ꢁO and
CH2CH2CH3), 2.05–2.15 (m, 24H, –CH2P), 4.22 (t, JHH
¼
Cꢁ ꢁ ꢁO bond lengths and distances, respectively. Within the
New J. Chem., 2003, 27, 150–154
153
Tao, Chi-Hang
