Inorganic Chemistry
Article
MHz, CDCl3, room temperature): δ −106.6 (s, 8F), −132.4 (s, 4F).
31P{1H} NMR (128 MHz, CDCl3, room temperature): δ −21.6 (br
s). UV/vis (CH2Cl2, room temperature): λmax 468 nm (ε = 1.8 × 103
M−1 cm−1). Anal. Calcd for C58H40Cl2Cu2F12P4: C, 54.14; H, 3.13.
Found: C, 54.03; H, 3.34.
NMR (400 MHz, CDCl3, room temperature): δ 6.88−7.96 (m, 35H).
19F NMR (376 MHz, CDCl3, room temperature): δ −104.4 (d, J =
270.0 Hz, 2F), −109.1 (d, J = 270.0 Hz, 2F), −130.1 (d, J = 232.0 Hz,
1F), −132.9 (d, J = 232.0 Hz, 1F). 31P{1H} NMR (128 MHz, CDCl3,
room temperature): not observed. UV/vis (CH2Cl2, room temper-
ature): λmax 426 nm (ε = 6.6 × 102 M−1 cm−1). Anal. Calcd for
C47H35CuF6IP3·CH2Cl2: C, 53.28; H, 3.45. Found: C, 53.18; H, 3.47.
Presence of CH2Cl2 molecules in the crystals was confirmed by X-ray
crystallographic analysis.
[CuBr(F6PP)]2 (1b). To a slurry of CuBr (0.14 g, 1.0 mmol) in
CH2Cl2 (50 mL) was added F6PP (0.55 g, 1.0 mmol), and the
resulting solution was stirred for 1 day. The solution was filtered and
evaporated. The residue was recrystallized from CH2Cl2 to afford 1b
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as orange crystals (0.69 g, 0.44 mmol, 88%). H NMR (400 MHz,
[Ag(F6PP)2](NO3) (4a). To a solution of AgNO3 (34 mg, 0.20
mmol) in MeOH (10 mL) was added a solution of F6PP (0.11 g, 0.20
mmol) in CH2Cl2 (10 mL), and the resulting solution was stirred for
1 day in the absence of light. The solution was filtered and
evaporated. The residue was recrystallized from CH2Cl2 to afford 4a
CDCl3, room temperature): δ 7.40 (dd, J = 6.5, 6.3 Hz, 16H), 7.27 (t,
J = 7.5 Hz, 8H), 7.13 (t, J = 7.5 Hz, 16H). 19F NMR (376 MHz,
CDCl3, room temperature): δ −106.5 (s, 8H), −132.2 (s, 4F).
31P{1H} NMR (128 MHz, CDCl3, room temperature): δ −23.7 (br
s). UV/vis (CH2Cl2, room temperature): λmax 462 nm (ε = 1.9 × 103
M−1 cm−1). Anal. Calcd for C58H40Br2Cu2F12P4: C, 50.64; H, 2.93.
Found: C, 50.71; H, 3.18.
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as yellow crystals (0.12 g, 0.093 mmol, 93%). H NMR (400 MHz,
CDCl3, room temperature): δ 7.12−7.32 (m, 40H). 19F NMR (376
MHz, CDCl3, room temperature): δ −105.3 (s, 8F), −132.5 (s, 4F).
31P{1H} NMR (128 MHz, CDCl3, room temperature): δ −17.9 (br
s). UV/vis (CH2Cl2, room temperature): λmax 378 nm (ε = 2.0 × 103
M−1 cm−1). Anal. Calcd for C58H40AgF12NO3P4: C, 55.35; H, 3.20.
Found: C, 55.22; H, 3.35.
[CuI(F6PP)]2 (1c). To a slurry of CuI (0.19 mg, 1.0 mmol) in
CH2Cl2 (65 mL) was added F6PP (0.55 g, 1.0 mmol), and the
resulting solution was stirred for 1 day in the absence of light. The
solution was filtered and evaporated. The residue was recrystallized
from CH2Cl2 to afford 1c as yellow crystals (0.66 g, 045 mmol, 90%).
1H NMR (400 MHz, CDCl3, room temperature): δ 7.38 (dd, J = 6.0,
[Ag(F6PP)2](PF6) (4b). To a solution of [Ag(F6PP)2](NO3) (4a;
30 mg, 0.024 mmol) in CH2Cl2 (5 mL) was added NH4PF6 (3.9 mg,
0.024 mmol), and the resulting solution was stirred for 1 day in the
absence of light and extracted with CH2Cl2. The organic layer was
dried over anhydrous MgSO4, filtered, and concentrated under
reduced pressure. The residue was recrystallized from CHCl3 to afford
4b as yellow crystals (26 mg, 0.019 mmol, 79%). 1H NMR (400 MHz,
CDCl3, room temperature): δ 7.19−7.26 (m, 40H). 19F NMR (376
MHz, CDCl3, room temperature): δ −73.6 (d, J = 714.0 Hz, 6F, PF6),
−105.7 (s, 8F), −133.1 (s, 4F). 31P{1H} NMR (128 MHz, CDCl3,
room temperature): not observed. UV/vis (CH2Cl2, room temper-
ature): λmax 376 nm (ε = 2.1 × 103 M−1 cm−1). Anal. Calcd for
C58H40AgF18P5: C, 51.92; H, 3.01. Found: C, 52.14; H, 3.25.
[Ag(F6PP)(OTf)]2 (5). To a solution of F6PP (54 mg, 0.10 mmol)
in Et2O (5 mL) was added AgOTf (26 mg, 0.10 mmol), and the
resulting solution was stirred for 1 day in the absence of light. The
solution was filtered and evaporated. The residue was recrystallized
from CH2Cl2 to afford 5 as yellow crystals (74 mg, 0.046 mmol, 92%).
1H NMR (400 MHz, CDCl3, room temperature): δ 7.34−7.43 (m,
24H), 7.30 (t, J = 7.2 Hz, 16H). 19F NMR (376 MHz, CDCl3, room
temperature): δ −77.0 (s, 6F, CF3SO3), −105.1 (s, 8F), −132.5 (s,
4F). 31P{1H} NMR (128 MHz, CDCl3, room temperature): δ −13.8
(s). UV/vis (CH2Cl2, room temperature): λmax 376 nm (ε = 2.5 × 102
M−1 cm−1). Anal. Calcd for C60H40Ag2F18O6P4S2: C, 44.97; H, 2.52.
Found: C, 44.86; H, 2.75.
5.8 Hz, 16H), 7.27 (t, J = 7.6 Hz, 8H); 7.12 (t, J = 7.6 Hz, 16H). 19
F
NMR (376 MHz, CDCl3, room temperature): δ −106.5 (s, 8F),
−132.2 (s, 4F). 31P{1H} NMR (128 MHz, CDCl3, room temper-
ature): δ −27.1 (br s). UV/vis (CH2Cl2, room temperature): λmax 454
nm (ε = 1.3 × 103 M−1 cm−1). Anal. Calcd for C58H40Cu2F12I2P4: C,
47.40; H, 2.74. Found: C, 47.76; H, 2.91.
[CuCl(F6P)]4 (2a). To a slurry of CuCl (0.10 g, 1.0 mmol) in
CH2Cl2 (65 mL) was added F6P (0.20 g, 0.50 mmol), and the
resulting solution was stirred for 1 day. The solution was filtered and
evaporated. The residue was recrystallized from CH2Cl2 to afford 2a
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as yellow crystals (0.23 g, 0.12 mmol, 96%). H NMR (400 MHz,
CDCl3, room temperature): δ 7.76 (dd, J = 7.8, 4.6 Hz, 16H), 7.45 (t,
J = 7.3 Hz, 8H), 7.36 (t, J = 7.6 Hz, 16H). 19F NMR (376 MHz,
CDCl3, room temperature): δ −104.2 (s, 8F), −114.0 (s, 8F), −130.0
(s, 8F). 31P{1H} NMR (128 MHz, CDCl3, room temperature): δ
−17.3 (br s). UV/vis (CH2Cl2, room temperature): λmax 344 nm (ε =
6.5 × 103 M−1 cm−1). Anal. Calcd for C68H40Cl8Cu4F24P4: C, 41.36;
H, 2.04. Found: C, 41.52; H, 2.34.
[CuBr(F6P)]4 (2b). To a slurry of CuBr (0.14 g, 1.0 mmol) in
CH2Cl2 (65 mL) was added F6P (0.20 g, 0.50 mmol), and the
resulting solution was stirred for 1 day. The solution was filtered and
evaporated. The residue was recrystallized from CH2Cl2 to afford 2b
1
as yellow crystals (0.26 g, 0.12 mmol, 96%). H NMR (400 MHz,
CDCl3, room temperature): δ 7.76 (dd, J = 7.8, 4,6 Hz, 16H), 7.47 (t,
J = 7.3 Hz, 8H), 7.36 (t, J = 7.6 Hz, 16H). 19F NMR (376 MHz,
CDCl3, room temperature): δ −104.2 (s, 8F), −113.7 (s, 8F), −129.7
(s, 8F). 31P{1H} NMR (128 MHz, CDCl3, room temperature): δ
−20.3 (br s). UV/vis (CH2Cl2, room temperature): λmax 350 nm (ε =
6.4 × 103 M−1 cm−1). Anal. Calcd for C68H40Br4Cl4Cu4F24P4: C,
37.94; H, 1.87. Found: C, 38.93; H, 2.16.
[Au2Cl2(F6PP)] (6). To a solution of [AuCl(tht)] (64 mg, 0.20
mmol) in CH2Cl2 (5 mL) was added F6PP (54 mg, 0.10 mmol), and
the resulting solution was stirred for 1 day. The solution was filtered
and evaporated. The residue was recrystallized from CH2Cl2 to afford
6 as yellow crystals (95 mg, 0.094 mmol, 94%). 1H NMR (400 MHz,
CDCl3, room temperature): δ 7.56−7.61 (m, 12H), 7.47 (t, J = 7.5
Hz, 8H). 19F NMR (376 MHz, CDCl3, room temperature): δ −104.6
(t, J = 5.6 Hz, 4F), −132.8 (t, J = 5.6 Hz, 2F); 31P{1H} NMR (128
MHz, CDCl3, room temperature): δ 16.0 (s). UV/vis (CH2Cl2, room
temperature): λmax 368 nm (ε = 7.4 × 102 M−1 cm−1). Anal. Calcd for
C29H20Au2Cl2F6P2: C, 34.51; H, 2.00. Found: C, 33.99; H, 2.17.
[AuCl(F6P)] (7). To a solution of [AuCl(tht)] (45 mg, 0.14 mmol)
in CH2Cl2 (5 mL) was added F6P (55 mg, 0.14 mmol), and the
resulting solution was stirred for 1 day. The solution was filtered and
evaporated. The residue was recrystallized from CH2Cl2 to afford 7 as
[CuI(F6P)]4 (2c). To a slurry of CuI (0.19 g, 1.0 mmol) in CH2Cl2
(65 mL) was added F6P (0.20 g, 0.50 mmol), and the resulting
solution was stirred for 1 day in the absence of light. The solution was
filtered and evaporated. The residue was recrystallized from CH2Cl2
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to afford 2c as yellow crystals (0.27 g, 0.11 mmol, 88%). H NMR
(400 MHz, CDCl3, room temperature): δ 7.76 (dd, J = 7.9, 5.6 Hz,
16H), 7.66 (t, J = 7.4 Hz, 8H), 7.54−7.58 (m, 16H). 19F NMR (376
MHz, CDCl3, room temperature): δ −104.1 (s, 8F), −113.5 (s, 8F),
−129.5 (s, 8F). 31P{1H} NMR (128 MHz, CDCl3, room temper-
ature): δ −29.8 (br s). UV/vis (CH2Cl2, room temperature): λmax 364
nm (ε = 9.6 × 103 M−1 cm−1). Anal. Calcd for C68H40I4Cl4Cu4F24P4:
C, 34.90; H, 1.72. Found: C, 35.93; H, 1.82.
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colorless crystals (76 mg, 0.12 mmol, 86%). H NMR (400 MHz,
CDCl3, room temperature): δ 7.63−7.72 (m, 6H), 7.54−7.59 (m,
4H). 19F NMR (376 MHz, CDCl3, room temperature): δ −103.6 (s,
2F), −114.2 (s, 2F), −130.0 (s, 2F). 31P{1H} NMR (128 MHz,
CDCl3, room temperature): δ 16.1 (s). Anal. Calcd for
C17H10AuCl2F6P: C, 32.56; H, 1.61. Found: C, 32.74; H, 1.68.
Catalytic Hydration of Acetate 8. To a solution of 6 (30 mg,
0.030 mmol) was added a solution of acetate 8 (0.17 g, 1.0 mmol) in
1,4-dioxane (7.5 mL) and H2O (2.5 mL). After it was stirred at 25 °C
[CuI(F6PP)(PPh3)] (3). To a solution of [CuI(F6PP)]2 (1c; 38 mg,
0.026 mmol) in CH2Cl2 (5 mL) was added PPh3 (14 mg, 0.052
mmol), and the resulting solution was stirred for 1 day. The solution
was filtered and evaporated. The residue was recrystallized from
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CH2Cl2 to afford 3 as yellow crystals (46 mg, 0.046 mmol, 88%). H
C
Inorg. Chem. XXXX, XXX, XXX−XXX