200
N. Ohshiro et al. / Journal of Organometallic Chemistry 569 (1998) 195–202
similar to that for 5a. Recrystallization from ethanol
gave pure 5b as pale yellow crystals in 77% yield.
M.p. 235.5–236.0°C (decomp.); IR (KBr) 2102 cm−1
CꢀCPt), 20.65 (s, ArMe), 16.30 (vt, N=35 Hz,
PCH2CH3), 8.39 (s, PCH2CH3); 31P-NMR (CDCl3) l
11.78 (s,
JPt–P=2390 Hz); Anal. Calc. for
1
(wCꢀC); H-NMR (C6D6) l 3.16 (s, 9H, ArMe), 1.95–
C75H114P6Pt3: C, 50.41; H, 6.43; P, 10.40%. Found: C,
50.31; H, 6.42; P, 10.21%.
1.84 (m, 36H, PCH2CH3), 1.10−0.97 (dt, JP–H=16Hz,
J
H–H=8Hz, 54H, PCH2CH3); 13C-NMR (CDCl3) l
135.37 (s, Ar), 125.22 (s, Ar), 99.53 (s, CꢀCPt), 88.70 (t,
3.8. Synthesis of complex 8
JP–C=30 Hz, CꢀCPt), 20.40 (s, ArMe), 14.36 (vt,
N=34 Hz, PCH2CH3), 8.02 (s, PCH2CH3); 31P-NMR
(CDCl3) l 15.34 (s, JPt–P=2407 Hz); Anal. Calc. for
C51H99P6Cl3Pt3: C, 38.53; H, 6.28; P, 11.69; Cl, 6.71%.
Found: C, 38.32; H, 6.12; P, 11.45; Cl, 6.71%.
A mixture of 4 (8.2 mg, 0.042 mmol) and 5a (800 mg,
0.382 mmol) in 70 ml of diethylamine was stirred at
room temperature in the presence of a copper chloride
catalyst for 1 h. Then a solution of phenylacetylene
(143 mg, 1.400 mmol) in 30 ml of diethylamine was
added to the reaction mixture. After stirred at room
temperature for 2 h, workup similar to that of 6a gave
8 as pale yellow oil (56 mg, 20%).
3.6. Synthesis of complex 6a
Complex 5a (1060 mg, 0.506 mmol) was reacted with
phenylacetylene (207 mg, 2.024 mmol) in 25 ml of
diethylamine in the presence of a copper chloride cata-
lyst at room temperature for 3 h. The solvent was then
removed under reduced pressure. After the residue was
extracted with benzene, the solution was dried over
anhydrous sodium sulfate followed by filtration using
alumina short column. The pale yellow filtrate was
concentrated under reduced pressure. Recrystallization
from ethanol gave pale yellow crystals of 6a (951 mg,
82%).
IR (neat) 2096 cm−1 (wCꢀC); H-NMR (CD2Cl2) l
7.26–7.09 (m, 30H, Ph), 2.58–2.56 (m, 36H, ArMe),
2.10–2.08 (m, 108H, PCH2CH2CH2CH3), 1.61–1.59
(m, 108H, PCH2CH2CH2CH3), 1.49–1.38 (m, 108H,
1
PCH2CH2CH2CH3),
0.94–0.86
(m,
162H,
PCH2CH2CH2CH3); 13C-NMR (CDCl3) l 135.53 (s,
Ar), 135.28 (s, Ar), 135.13 (s, Ar), 130.93 (s, Ar), 129.28
(s, Ar), 127.79 (s, Ar), 125.70 (s, Ar), 125.42 (s, Ar),
125.29 (s, Ar), 124.67 (s, Ar), 114.58 (t, JP–C=30 Hz,
CꢀCPt), 113.54 (t, JP–C=29 Hz, CꢀCPt), 113.45 (t,
1
M.p. 77.5–78.0°C; IR (KBr) 2106 cm−1 (wCꢀC); H-
J
J
P–C=31 Hz, CꢀCPt), 109.42 (s, CꢀCPt), 108.69 (t,
P–C=28 Hz, CꢀCPt), 107.40 (s, CꢀCPt), 106.93 (s,
NMR (CD2Cl2) l 7.26–7.07 (m, 15H, Ph), 2.57 (s, 9H,
ArMe), 2.18–2.04 (m, 36H, PCH2CH2CH2CH3), 1.66–
1.57 (m, 36H, PCH2CH2CH2CH3), 1.50–1.36 (m, 36H,
PCH2CH2CH2CH3), 0.92 (t, J=7.3Hz, 54H,
PCH2CH2CH2CH3); 13C-NMR (CDCl3) l 135.45 (s,
Ar), 130.93 (s, Ar), 129.22 (s, Ar), 127.78 (s, Ar), 125.40
(s, Ar), 124.68 (s, Ar), 113.95 (t, JP–C=31 Hz, CꢀCPt),
109.47 (s, CꢀCPt), 108.56 (t, JP–C=28 Hz, CꢀCPt),
106.41 (s, CꢀCPt), 26.55 (s, ArMe), 24.39 (vt, N=13
Hz, PCH2CH2CH2CH3), 23.78 (vt, N=34 Hz,
PCH2CH2CH2CH3), 20.81 (s, PCH2CH2CH2CH3),
13.91 (s, PCH2CH2CH2CH3); 31P-NMR (CDCl3) l 3.77
(s, JPt–P=2375 Hz); Anal. Calc. for C111H186P6Pt3: C,
58.17; H, 8.18; P, 8.11%. Found: C, 58.03; H, 8.00; P,
8.05%.
CꢀCPt), 106.69 (s, CꢀCPt), 26.54 (s, ArMe), 24.40 (vt,
N=14 Hz, PCH2CH2CH2CH3), 24.27 (s, ArMe), 23.84
(vt, N=34 Hz, PCH2CH2CH2CH3), 23.76 (s, ArMe),
20.97
(s,
PCH2CH2CH2CH3),
13.91
(s,
PCH2CH2CH2CH3); 31P-NMR (CDCl3) l 4.20 (s, JPt–
P=2396Hz, 3P), 3.80 (s, JPt–P=2375Hz, 6P); Anal.
Calc. for C324H552P18Pt9: C, 57.56; H, 8.23; P, 8.25%.
Found: C, 57.65; H, 8.11; P, 7.99%.
3.9. Synthesis of complex 9
The reaction of 4 (826 mg, 4.297 mmol) with 5a
(1000 mg, 0.477 mmol) by a procedure similar to that
for 6a gave 9 (850 mg, 70%) as pale yellow crystals.
M.p. 133.5–134.5°C; IR (KBr) 2090 cm−1 (wCꢀC),
1
3.7. Synthesis of complex 6b
3311 cm−1 (wꢀC–H); H-NMR (C6D6) l 3.13–3.10 (m,
36H, ArMe), 2.78 (s, 6H, ꢀCH), 2.12–2.09 (m, 36H,
PCH2CH2CH2CH3), 1.71–1.67 (m, 36H, PCH2CH2-
CH2CH3), 1.47–1.33 (m, 36H, PCH2CH2CH2CH3),
0.93 (t, J=7.3Hz, 54H, PCH2CH2CH2CH3); 13C-NMR
(CDCl3) l 141.64 (s, Ar), 138.91 (s, Ar), 135.40 (s, Ar),
127.03 (s, Ar), 125.33 (s, Ar), 119.30 (s, Ar), 118.86 (t,
Complex 6b was prepared from the reaction of 5b
with phenylacetylene by a method similar to that for 6a
in 83% yield.
M.p. 237.0–237.5°C (decomp.); IR (KBr) 2106 cm−1
(wCꢀC); 1H-NMR(CDCl3) l 7.30–7.17 (m, 15H, Ph),
2.58 (s, 9H, ArMe), 2.18–2.09 (m, 36H, PCH2CH3),
J
P–C=29 Hz, CꢀCPt), 113.17 (t, JP–C=30 Hz,
1.25–1.14 (dt,
JP–H=16Hz,
J
H–H=8Hz, 54H,
CꢀCPt), 107.17 (s, CꢀCPt), 105.80 (s, CꢀCPt), 84.02 (s,
CꢀC), 81.85 (s, CꢀC), 26.55 (s, ArMe), 24.34 (vt,
N=13 Hz, PCH2CH2CH2CH3), 23.94 (vt, N=34 Hz,
PCH2CH2CH2CH3), 20.99 (s, ArMe), 20.61 (s,
PCH2CH2CH2CH3), 19.75 (s, ArMe), 13.90 (s,
PCH2CH3); 13C-NMR (CDCl3) l 135.67 (s, Ar), 130.92
(s, Ar), 129.09 (s, Ar), 127.87 (s, Ar), 125.43 (s, Ar),
124.82 (s, Ar), 114.19 (t, JP–C=30 Hz, CꢀCPt), 109.45
(s, CꢀCPt), 108.22 (t, JP–C=29 Hz, CꢀCPt), 107.56 (s,