Inorganic Chemistry
Article
1b and 1c were obtained by slow evaporation from chloroform/n-
hexane solutions.
9.04 (t, J = 4.75 Hz, 1H), 8.89 (t, J = 4.64 Hz, 1H). 19F-NMR (377
MHz, CDCl3): δ = −33.86 (d, J = 846.40 Hz, 2F), −136.13 −
−136.33 (m, 6 F, ortho-F), −149.69 (t, J = 21.02 Hz, 1F, para-F),
−149.88 (t, J = 21.04 Hz, 1F, para-F), −150.37 (t, J = 20.98 Hz, 1F,
para-F), −160.76 − −161.34 (m, 6F, meta-F). 31P NMR: −179.77 (t,
J = 842.52 Hz, 1P). MS+(APCI, positive mode) for C37H3Br5F17N4P:
m/z = 1255.5700 (calculated), 1257.5679 (calculated), 1255.5659
(observed), 1257.5640 (observed). UV−vis (toluene) λmax (ε) [nm
(× 104 cm−1 M−1)]: 399 (5.4), 420 (24), 542 (1.7), 586 (3.2).
Synthesis of Bis-CF3-Substituted Complex 2. A flask loaded with a
DMF solution (5 mL) of 1b (30 mg, 31 μmol) and copper(I) iodide
(0.17 g, 0.93 mmol) (Aldrich) was heated and stirred at 100 °C under
an argon atmosphere for 15 min. Then, methyl 2,2-difluoro-2-
(fluorosulfonyl) acetate (0.12 mL, 0.93 mmol) was added into this
solution. After reaction for 10 h, the solvent was evaporated and the
reaction residue was redissolved in dichloromethane (25 mL) and was
washed by distilled water three times. Then, after filtration,
evaporation of the organic phase reduced the reaction mixture to a
residue which was then dissolved into a very small amount of
dichloromethane for use with PLC (preparative layer plate) in which
n-hexane:ethyl acetate (7:1 by weight) was used as the eluent. The
target compound was collected from the PLC. The scratched silica
powder was suspended in a small amount of dichloromethane and
then filtrated. A pure reddish product was then obtained after
evaporation. The Rf values and isolated yield of 2 were mentioned
below: 2 (0.58, 10%). X-ray quality crystals of 2 were obtained by
Alternative Method for the Synthesis of Mono-CF3-Substituted
Complex 1b. A 5 mL vial was equipped with a magnetic stir bar and
was charged with a solution of (tpfc)PF2 (50 mg, 52 μmol),
Umemoto’s reagent (36 mg, 104 μmol), and NMM (12 μL, 104
μmol) in DMF (2 mL). After stirring at room temperature for 1 h, the
mixture was added into a separatory funnel containing a mixture of
H2O (10 mL) and Et2O (10 mL). The aqueous layer was washed by
Et2O (3 × 15 mL). The organic phase portions were merged and
dried with anhydrous sodium sulfate. The crude product/residue was
then purified by flash chromatography on silica gel (eluent:dichloro-
methane: n-hexane = 1:4) to obtain a reddish product carefully
characterized as 1b (see main text).
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1a: H NMR (400 MHz, CDCl3): δ = 9.53 (t, J = 3.70 Hz, 1H),
9.17 (d, J = 4.50 Hz, 1H), 9.09−9.02 (m, 3H), 8.89−8.86
(overlapping doublets, 2H). 19F-NMR (377 MHz, CDCl3): δ =
−37.37 (d, J = 826.57 Hz, 2F), −54.17 (s, 3F), −135.90 − −136.39
(m, 6 F, ortho-F), −150.05 (t, J = 20.90 Hz, 1F, para-F), −150.
Twenty-five (t, J = 22.62 Hz, 1F, para-F), −150.55 (t, J = 22.62 Hz,
1F, para-F), −159.69 − −160.57 (m, 6F, meta-F). 31P NMR: −181.07
(t, J = 826.57 Hz, 1P). MS−(APCI, negative mode) for C38H7F20N4P:
m/z = 930.0089 (calculated), 930.0705 (observed). UV−vis
(toluene) λmax (ε) [nm (× 104 cm−1 M−1)]: 385 (2.80), 406
(15.42), 576 (1.93).
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1b: H NMR (400 MHz, CDCl3): δ = 9.82 (d, J = 3.62 Hz, 1H),
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9.48 (t, J = 3.27 Hz, 1H), 9.09 (t, J = 4.80 Hz, 1H), 9.06 (t, J = 5.31
Hz, 1H), 8.92 (t, J = 4.97 Hz, 1H), 8.88−8.85 (overlapping doublets,
2H). 19F-NMR (377 MHz, CDCl3): δ = −36.88 (d, J = 827.36 Hz,
2F), −53.36 (s, 3F), −135.57 − −136.37 (m, 6 F, ortho-F), −150.22
(t, J = 22.86 Hz, 1F, para-F), −150.49 (t, J = 22.06 Hz, 1F, para-F),
−150.70 (t, J = 21.35 Hz, 1F, para-F), −159.68 − −162.54 (m, 6F,
meta-F). 31P NMR: −180.02 (t, J = 827.36 Hz, 1P). MS− (APCI,
negative mode) for C38H7F20N4P: m/z = 930.0089 (calculated),
929.9489 (observed). UV−vis (toluene) λmax (ε) [nm (× 104 cm−1
M−1)]: 385 (5.22), 406 (27.26), 564 (2.84), 576 (2.88).
slow evaporation from chloroform/n-hexane solutions. 2: H NMR
(400 MHz, CDCl3): δ = 9.78 (d, J = 3.60 Hz, 2H), 8.94 (t, J = 4.90
Hz, 2H), 8.85 (t, J = 4.05 Hz, 2H). 19F-NMR (377 MHz, CDCl3): δ =
−36.69 (d, J = 836.62 Hz, 2F), −53.62 (s, 6F), −134.56 − −137.53
(m, 6F, ortho-F), −149.09 (t, J = 23.07 Hz, 1F, para-F), −149.92 (t, J
= 23.51 Hz, 2F, para-F), −159.96 (m, 2F, meta-F), −161.79 (m, 4F,
meta-F). 31P NMR: −179.46 (t, J = 838.01 Hz, 1P).MS+ (APCI,
positive mode) for C39H6F23N4P: m/z = 997.9963 (calculated),
997.9906 (observed). UV−vis (toluene) λmax (ε) [nm (× 104 cm−1
M−1)]: 386 (5.29), 407 (26.20), 569 (3.73), 578 (3.62).
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1c: H NMR (400 MHz, CDCl3): δ = 9.52 (t, J = 3.20 Hz, 1H),
Synthesis of Multi-CF3 Substituted Complexes 3, 4, and 5. A flask
loaded with a DMF solution (5 mL) of P-Br5 (50 mg, 36 μmol) and
copper(I) iodide (0.200 g, 1.08 mmol) (Aldrich) was heated and
stirred at 100 °C under argon atmosphere for 15 min. Then, methyl
2,2-difluoro-2-(fluorosulfonyl)acetate (0.14 mL, 1.08 mmol) was
added into this solution. After reaction for 20 h, the solvent was
evaporated and the reaction residue was redissolved in dichloro-
methane (25 mL) and was washed by distilled water three times.
Then, after filtration and evaporation of the organic phase, the
reaction mixture was dissolved by a very small amount of
dichloromethane to enable a transfer onto PLC (preparative layer
plates) in which n-hexane:ethyl acetate (7:1 by weight) was used as
the eluent. Three bluish target compounds were collected from the
PLC with silica format in different bands with different Rf values. The
scratched silica powder was dissolved in a small amount of
dichloromethane and filtrated. Pure reddish products were obtained
after evaporation. The Rf values and isolated yields of 3, 4, and 5 were
measured as 3 (0.36, 2%), 4 (0.29, 3%), and 5 (0.58, 8%). The X-ray
quality crystal of 5 were grown by slow evaporation from chloroform/
n-hexane solutions.
9.48 (t, J = 3.13 Hz, 1H), 9.28 (d, J = 4.48, 1H), 9.08 (t, J = 4.93 Hz,
1H). 9.05 (t, J = 4.42 Hz, 1H), 8.91 (t, J = 4.23, 1H), 8.87 (t, J = 4.54,
1H). 19F-NMR (377 MHz, CDCl3): δ = −36.90 (d, J = 828.90 Hz,
2F), −53.24 (s, 3F), −136.42 (ddd, J = 29.30, 29.20, 17.70 Hz, 6F,
ortho-F), −150.02 − −151.40 (m, 3F, para-F), −160.61 (dd, J =
23.20, 8.30 Hz, 4F, meta-F), −162.85 (td, J = 24.80, 9.40 Hz, 2F,
meta-F). 31P NMR: −182.47 (t, J = 828.90 Hz, 1P). MS−(APCI,
negative mode) for C38H7F20N4P: m/z = 930.0089 (calculated),
929.9924 (observed). UV−vis (toluene) λmax (ε) [nm (× 104 cm−1
M−1)]: 388 (3.75), 409 (23.68), 558 (1.23), 580 (1.37).
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1d: H NMR (400 MHz, CDCl3): δ = 9.54 (t, J = 5.60 Hz, 2H),
9.44 (d, J = 5.30 Hz, 1H), 9.09−9.04 (m, 3H), 8.75 (t, J = 4.60 Hz,
1H). 19F-NMR (377 MHz, CDCl3): δ = −36.98 (d, J = 827.45 Hz,
2F), −53.27 (s, 3F), −135.89 (d, J = 24.81 Hz, 2F, ortho-F), −136.19
(m, 4F, ortho-F), −149.96 (t, J = 23.19 Hz, 1F, para-F), −150.44 (t, J
= 21.32 Hz, 1F, para-F), −150.94 (t, J = 21.57 Hz, 1F, para-F),
−160.13 (m, 2F, meta-F), −160.42 (m, 2F, meta-F), −162.73 (m, 2F,
meta-F). 31P NMR: −181.79 (t, J = 827.45 Hz, 1P). MS−(APCI,
negative mode) for C38H7F20N4P: m/z = 930.0089 (calculated),
929.9807 (observed). UV−vis (toluene) λmax (ε) [nm (× 104 cm−1
M−1)]: 389 (2.41), 410 (17.13), 554 (0.64), 580 (0.78).
Synthesis of Pentabrominated P-Br5. (tpfc)PF2 (50 mg, 52
μmol) and 1 mL of Br2 solution were introduced into a 25 mL round
flask containing a magnetic stirrer. Then, ca. 15 mL of methanol was
added before stirring was commenced. After 10 h, this reaction
mixture was first diluted with 100 mL of dichloromethane and then
evaporated down to a residue. The residue was chromatographed on a
silica gel column (eluent:dichloromethane: hexane = 1:3) to give the
corrole product as the first red eluate. Then, this fraction was
evaporated and dried/precipitated to afford red crystals (yield: 60%)
through a recrystallization step using the solvent mixture (dichlor-
omethane:hexane = 1:1). The X-ray structural information is shown
below. 1H NMR (400 MHz, CDCl3): δ = 9.17 (d, J = 4.84 Hz, 1H),
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3: H NMR (400 MHz, CDCl3): δ = 9.07 (d, J = 4.76 Hz, 1H),
8.93 (t, J = 4.09 Hz, 1H), 8.72−8.64 (m, 3H). 19F-NMR (377 MHz,
CDCl3): δ = −36.84 (d, J = 839.74 Hz, 2F), −49.10 (q, J = 12.90 Hz,
3F), −50.08 (m, 3F), −53.78 (overlapping doublets, 3F), −136.09
(m, 6F, ortho-F), −148.37 (t, J = 20.09 Hz, 1F, para-F), −149.05 (t, J
= 22.21 Hz, 1F, para-F), −149.48 (t, J = 24.20 Hz, 1F, para-F),
−159.09 (m, 2F, meta-F), −159.49 (m, 2F, meta-F), −161.46 (m, 2F,
meta-F). 31P NMR: −180.43 (t, J = 841.32 Hz, 1P). MS− (APCI,
negative mode) for C40H5F26N4P: m/z = 1065.9837 (calculated),
1066, 903 (observed). UV−vis (toluene) λmax (ε) [nm (× 104 cm−1
M−1)]: 389 (3.8), 408 (11.33), 544 (0.85), 587 (2.92).
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4: H NMR (400 MHz, CDCl3): δ = 8.66 (t, J = 4.80 Hz, 2H),
8.51 (t, J = 4.41 Hz, 2H). 19F-NMR (377 MHz, CDCl3): δ = −34.40
(d, J = 850.84 Hz, 2F), −49.47 (s, 6F), −50.15 (s, 6F), −136.16 (m,
K
Inorg. Chem. XXXX, XXX, XXX−XXX