Article
Inorganic Chemistry, Vol. 50, No. 5, 2011 2017
3
(0.25 g, 60%). ESI-MS: 681.3. 31P{1H} NMR (CDCl3): 34.64 (s).
(CDCl3): δ 182.40 (s, CCHO), 146.14 (s, CTh-5 ), 144.80 (d, | JCP
|
00
13C{1H} NMR (CDCl3): δ 145.47 (d, |3JCP| 5.1 Hz, CTh-2), 137.66
2
5.3 Hz, CTh-2), 142.04 (s, CTh-2 or 5 or 2 ), 137.67 (d, | JCP| 8.9 Hz,
0
0
00
(d, |2JCP| 8.7 Hz, CTh-4), 136.13 (d, |4JCP| 1.6 Hz, CTh-2 ), 134.32 (d,
0
00
CTh-4), 137.31 (s, CTh-3 ), 137.27 (s, CTh-2
0
or 50 or 200
), 136.10 (s,
|
|1JCP| 92.1 Hz, CTh-5), 133.22 (d, |1JCP| 89.6 Hz, CPh-i), 131.92 (d,
CTh-2 or 5 or 2 ), 133.34 (d, | JCP| 110.0 Hz, CTh-5), 132.49 (d, |1JCP
1
0
0
00
|4JCP| 3.0 Hz, CPh-p), 131.78 (d, |2JCP| 11.3 Hz, CPh-o), 128.62 (d,
110.2 Hz, CPh-i), 132.40 (d, |4JCP| 2.7 Hz, CPh-p), 131.80 (d, |2JCP
|
3
|3JCP| 13.1 Hz, CPh-m), 125.92 (s, CTh-3 ), 124.77 (d, | JCP| 12.9 Hz,
10.4 Hz, CPh-o), 128.63 (d, |3JCP| 12.7 Hz, CPh-m), 126.95(s, CTh-3 or
0
0
CTh-3). 1H NMR (CDCl3): 7.82-7.76 (m, 8H, HPh-o), 7.54-7.45 (m,
0
00
3
4 ), 126.14 (s, CTh-4 ), 125.12 (d, | JCP| 12.7 Hz, CTh-3), 124.51 (s,
12H, HPh-p and m), 7.32-7.26 (dd, 2H, |3JPH| 8.2 Hz, |3JHH| 3.8 Hz,
0
0
1
C
Th-3 or 4 ). HNMR(CDCl3):9.87(1H, s, HCHO), 7.81-7.74 (4H,
H
Th-4), 7.18-7.16 (dd, 2H, |3JHH| 3.8 Hz, |4JPH| 1.8 Hz, HTh-3),
00
m, CPh-o), 7.68 (1H, d, |3JHH| 3.8 Hz, HTh-3 ), 7.61-7.59 (2H, m,
CPh-p), 7.53-7.50 (4H, m, CPh-m), 7.35 (1H, dd, |3JPH| 7.5 Hz,
7.10 (s, 2H, HTh-3 ). UV-vis (CH2Cl2): λmax/nm (ε/dm3 mol-1
0
3
3
cm-1) = 377 (19300). Anal. Calcd for [C36H26P2S5]: C, 63.51; H,
3.85. Found: C, 63.06; H, 4.19.
|3JHH| 3.8 Hz, HTh-4), 7.28-7.17 (3H, m, HTh-3 and HTh-3 and
0
3
0
00
H
Th-4 ), 7.17 (1H, d, | JHH| 3.8 Hz, HTh-4 ). UV-vis (CH2Cl2):
5,500-Bis(diphenylmethylphosphino)-2,20:50,200-terthiophene Io-
dide, [Ph2(Me)P(C4H2S)3P(Me)Ph2]I2, 4. Excess CH3I (1.0 mL)
was added to a solution of 1 (0.30 g, 0.49 mmol) in CH2Cl2 (30 mL).
The reaction mixture was stirred at room temperature overnight
and then was evaporated under reduced pressure to give a yellow
solid residue. Recrystallization from CH3CN/Et2O yielded the ana-
lytically pure product as a yellow crystalline solid (0.35 g, 80%).
31P{1H} NMR (CD3CN): 16.97 (s). 13C{1H} NMR (CD3CN): δ
λ
max/nm (ε/dm3 mol-1 cm-1) = 401 (37000). Anal. Calcd for
3
3
[C25H17O2PS3]: C, 63.01; H, 3.60. Found: C, 62.79; H, 3.67.
500-Hydroxymethyl-5-(diphenyloxophosphino)-2,20:50,200-terthio-
phene, Ph2(O)P(C4H2S)3CH2OH, 8. Sodium borohydride (0.010 g,
0.26 mmol) was added to a stirred solution of 7(0.050 g, 0.10 mmol)
in 10 mL of dry THF under nitrogen at ambient temperature. The
reaction mixture was stirred overnight and then the THF was
evaporated, water was added, and the mixture was stirred for 1 h.
The resultant yellow precipitate was collected by filtration, and
dried. Recrystallization from hexanes-ethyl acetate afforded the
analytically pure product as yellow crystals (0.045 g, 90%). ESI-
MS: 478.9. 31P{1H} NMR (CDCl3): 23.04 (s). 13C{1H} NMR
148.66 (d, |3JCP| 5.7 Hz, CTh-2), 142.73 (d, |2JCP| 9.6 Hz, CTh-4),
4
135.33 (d, |4JCP| 1.9 Hz, CTh-2 ), 135.09 (d, | JCP| 3.1 Hz, CPh-p),
0
132.67 (d, |2JCP| 11.5 Hz, CPh-o or m), 129.84 (d, |3JCP| 13.4 Hz,
3
Ph-m or o), 127.97 (s, CTh-3 ), 126.86 (d, | JCP|13.9Hz, CTh-3), 119.39
0
C
(d, |1JCP| 92.0 Hz, CTh-5), 116.13 (d, |1JCP| 103.8 Hz, CPh-i), 9.88 (d,
|1JCP| 59.1 Hz, CCH3). 1H NMR (CD3CN): 7.95-7.90 (m, 4H, HPh
(CDCl3): δ 145.80 (d, |3JCP| 5.5 Hz, CTh-2), 144.50 (s, CTh-5 ),
00
2
138.01 (s, CTh-2 or 5 or 2 ), 137.78 (d, | JCP| 9.1 Hz, CTh-4), 136.50 (s,
0
0
00
and HTh-4), 7.87-7.74 (m, 18H, HPh), 7.67-7.65 (dd, 2H, |3JHH|4.0
1
0
0
00
0
0
00
CTh-2 or 5 or 2 ), 134.28 (s, CTh-2 or 5 or 2 ), 132.44 (d, | JCP| 110.0
Hz, CPh-i), 132.35 (d, |4JCP| 2.7 Hz, CPh-p), 131.70 (d, |1JCP| 110.7
Hz, CTh-5), 131.81 (d, |2JCP| 10.4 Hz, CPh-o), 128.61 (d, |3JCP| 12.7
Hz, |4JPH| 2.2 Hz, HTh-3), 7.47 (s, 2H, HTh-3 ), 2.96 (d, 6H, | JPH| 14
2
0
Hz, HCH3). UV-vis (CH3CN): λmax/nm (ε/dm3 mol-1 cm-1) =
3
3
387 (35500). Anal. Calcd for [C38H32P2S3I2 H2O]: C, 49.68; H, 3.73.
Found: C, 49.60; H, 3.60.
00
0
00
0
or 30
or 4 ),
), 123.70 (s,
or 30
Hz, CPh-m), 125.89 (s, CTh-4
or 4 ), 125.87 (s, CTh-4
124.28 (d, |3JCP| 12.8 Hz, CTh-3), 124.25 (s, CTh-4
0
or 300
5-(Diphenyloxophosphino)-2,20:50,200-terthiophene, Ph2(O)P-
(C4H2S)3H, 6. Excess H2O2-urea pellets (4.0 g) were added to
a solution of 5 (1.32 g, 3.05 mmol) in CH3OH (300 mL). The reac-
tion mixture was stirred at room temperature overnight and then
was evaporated to dryness under reduced pressure to give a solid
residue. This residue was purified by column chromatography
(Et2O eluent) to yield the analytically pure product as a yellow
crystalline solid (1.15 g, 85.1%). ESI-MS: 449.0 [Mþ]. 31P{1H}
CTh-4 or 3 ), 60.02 (s, CCH2). 1H NMR(CDCl3):7.78-7.73 (4 H, m,
HPh-o), 7.62-7.56 (2H, m, HPh-p), 7.51-7.48 (4H, m, HPh-m), 7.26
(1H, dd, |3JPH|7.8Hz, |3JHH|3.8Hz, HTh-4), 7.15 (1H, dd, |4JPH|1.9
0
00
Hz, |3JHH| 3.8 Hz, HTh-3), 7.05 (1H, d, |3JHH| 3.9 Hz, HTh-3 or 4 ),
0
0
6.98 (2H, d, |3JHH| 3.8 Hz, HTh-3
0
00
and HTh-3 ), 6.86 (1H, d,
or 40
|3JHH| 3.5 Hz, HTh-4 ), 4.80 (2H, s, HCH2). UV-vis (CH2Cl2):
00
λ
max/nm (ε/dm3 mol-1 cm-1) = 377 (21300). Anal. Calcd for
3
3
[C25H19O2PS3]: C, 62.74; H, 4.00. Found: C, 62.28; H, 3.91.
5-(Diphenyloxophosphino)-2,20:50,200-terthiophene-500-carboxy-
lic Acid,Ph2(O)P(C4H2S)3COOH, 9. A mixture of Ag2O (2.0 g,
8.6 mmol) in water (10 mL) was added to a solution of NaOH
(1.0 g, 25 mmol) in water (10 mL) at room temperature. After this
mixture was stirred for 15 min, a solution of 7 (0.20 g, 0.42 mmol) in
THF (50 mL) was slowly added. The reaction mixture was stirred at
room temperature for 0.5 h, and then was refluxed for 2 days. Next,
the reaction mixture was acidified to pH = 4 with 10% aqueous
HCl solution. The resulting brown precipitate was collected by
filtration and washed with methanol. The filtrate and washings were
combined and evaporated under reduced pressure to give a solid
residue. The residue was purified by column chromatography with
ethyl acetate as the eluent to yield the analytically pure product as an
orange powder (0.12 g, 58%). ESI-MS: 492.9. 31P{1H} NMR
(CD3OD): 24.11 (s). 1H NMR (CD3OD): 7.09-7.03 (m. 4H, HPh),
6.99-6.97 (m, 3H, HPh and HTh), 6.92-6.88 (m, 4H, HPh),
6.72-6.71 (m, 1H, HTh), 6.68-6.66 (m, 1H, HTh), 6.61-6.61(m,
2H, HTh), 6.58-6.57 (m, 1H, HTh).
NMR (CDCl3): 22.65 (s). 13C{1H} NMR (CDCl3): δ 145.73 (d,
2
|3JCP| 5.3 Hz, CTh-2), 137.93 (s, CTh-5 or 2 ), 137.73 (d, | JCP| 8.9 Hz,
0
00
4
0
00
0
CTh-4), 136.64 (s, CTh-5 or 2 ), 134.39 (d, | JCP| 1 Hz, CTh-2 ), 132.62
(d, |1JCP| 110.2 Hz, CPh-i), 132.01 (d, |1JCP| 111.6 Hz, CTh-5), 132.31
(d, |4JCP| 2.8 Hz, CPh-p), 131.83 (d, |2JCP| 10.4 Hz, CPh-o), 128.59 (d,
|3JCP| 12.7 Hz, CPh-m), 127.98 (s, CTh-4 ), 125.86 (s, CTh-3 or 4 ),
00
0
0
3
), 124.45 (s, CTh-3 or 4 ), 124.33 (d, | JCP| 12.8
00
0
0
or 500
125.01 (s, CTh-3
Hz, CTh-3), 124.15 (s, CTh-3
). 1H NMR (CDCl3): 7.80-
00
or 500
7.75 (m, 4H, HPh-o), 7.58-7.56 (m, 2H, HPh-p), 7.52-7.47 (m, 4H,
HPh-m), 7.36 (dd, 1H, |3JPH| 7.5 Hz, |3JHH| 3.8 Hz, HTh-4), 7.25 (dd,
1H, |3JHH| 5.1 Hz, |4JHH| 1.1 Hz, HTh-3
), 7.21 (dd, 1H, |4JPH
|
00
or 500
1.9 Hz, |3JHH| 3.8 Hz, HTh-3), 7.19 (m, 1H, HTh-3
), 7.13 (d, 1H,
0
00
or 500
|3JHH| 3.8 Hz, HTh-3 or 4 ), 7.08 (d, 1H, | JHH| 3.8 Hz, HTh-3 or 4 ),
3
0
0
0
7.03 (dd, 1H, |3JHH| 5.1 Hz, |3JHH| 3.6 Hz, HTh-4 ). UV-vis (CH2-
00
Cl2):λmax/nm (ε/dm3 mol-1 cm-1) = 368 (20500). Anal. Calcd for
3
3
[C24H17OPS3]: C, 64.26; H, 3.82. Found: C, 64.50; H, 4.01.
5-(Diphenyloxophosphino)-2,20:50,200-terthiophene-500-carbalde-
hyde, Ph2(O)P(C4H2S)3CHO, 7. Compound 6 (0.55 g, 1.2 mmol)
was dissolved in 50 mL of dry 1,2-dichloroethane under nitrogen
atmosphere. Excess DMF (2.0 mL) was first added to this
solution and then POCl3 (0.60 mL, 6.6 mmol) was added drop-
wise with stirring. The reactionmixture was heated at 60 °C under
nitrogen for 36 h and then was poured slowly into 100 mL of
saturated aqueous sodium acetate solution. This mixture was
stirred for 2 h, and then the organic layer was diluted with
CH2Cl2, separated, and washed with water. After evaporation
of the solvents, the solid residue was purified with silica gel flash
chromatography (hexanes-ethyl acetate 1:1) to yield the analy-
tically pure product as a yellow product (0.50 g, 86%). ESI-MS:
476.9. 31P{1H} NMR (CDCl3): 22.29 (s). 13C{1H} NMR
Methyl 5-(diphenyloxophosphino)-2,20:50,200-terthiophene-500-car-
boxylate, Ph2(O)P(C4H2S)3COOCH3, 10. Concentrated H2SO4
(1.0 mL) was added to a solution of 9 (0.10 g, 0.20 mmol) in
methanol (100 mL). The reaction mixture was stirred under reflux
overnight and then was evaporated under reduced pressure to give a
solid residue. The residue was washed with water and then was
purified by column chromatography (hexane-ethyl acetate, 1:1, v/v)
to yield the analytically pure product as a yellow solid (0.095 g,
90%). ESI-MS: 506.9. 31P{1H} NMR (CDCl3): 22.81 (s). 13C{1H}
NMR (CDCl3): δ 162.35 (s, CCdO), 145.08 (d, |3JCP| 5.5 Hz, CTh-2),
2
143.24 (s, CTh-5 ), 137.69 (d, | JCP| 8.8 Hz, CTh-4), 136.52 (s, CTh-5 ),
00
0
1
136.22 (d, |4JCP| 1 Hz, CTh-2 ), 134.30 (s, CTh-3 ), 132.93 (d, | JCP
|
0
00