Inorganic Chemistry
Article
dissolved in acetonitrile (4 mL, bubbled by N2). The solution was
heated at 65 °C under Ar for 3 days. The solution was cooled to
room temperature and was purified by ion-exchange chromatography
(SP Sephadex C-25, eluent: acetonitrile−water (1:1 v/v) containing
NH4PF6 (0−2 mM)). Some portion of acetonitrile was evaporated
under reduced pressure. The orange precipitate was filtered off and
washed with water and ether. Obtained products were used in the next
reaction without further purification. Yield: 37.0 mg (58%). FT-IR
(in CH2Cl2) νCO/cm−1: 1941, 1872. ESI−MS (in acetonitrile): m/z
2.55 (s, 24H), 2.50 (s, 6H). ESI−MS (in acetonitrile): m/z 327
−
−
−
([M-4PF6 ]4+), 484 ([M-3PF6 ]3+), 798 ([M-2PF6 ]2+). HRMS (ESI−
−
TOF): m/z [M-4PF6 ]4+ Anal. Calcd for C72H70N12Ru2: 326.5992.
Found: 326.5984.
Ru(CC)Ir3+. [Ru(dmb)2(Brbpy)](PF6)2 (11 mg, 11 μmol),
[Ir(ppy)2(4-ethynyl-bpy)](PF6) (8.8 mg, 11 μmol), PdCl2(PPh)2
(0.23 mg, 0.33 μmol), CuI (0.20 mg, 1.1 μmol), and diisopropylamine
(40 μL, 300 μmol) were dissolved in DMF (5 mL, bubbled by N2).
The solution was heated at 50 °C under Ar for 3 h. Additional
[Ir(ppy)2(4-ethynyl-bpy)](PF6) (8.8 mg, 11 μmol) was added to the
solution, and the solution was heated for another 3 h. After adding
[Ir(ppy)2(4-ethynyl-bpy)](PF6) (8.8 mg, 11 μmol), the solution was
heated overnight. The solution was cooled to room temperature and
was purified by ion-exchange chromatography (CM Sephadex C-25,
eluent: acetonitrile−water (1:1 v/v) containing NH4PF6 (0−8 mM)).
Some portion of acetonitrile was evaporated under reduced pressure.
The red precipitate was filtered off and washed with water and ether.
Yield: 7.4 mg (40%). 1H NMR (400 MHz, acetone-d6): δ 8.98 (s, 1H),
8.93 (s, 1H), 8.87 (d, J = 8.4 Hz, 1H), 8.83 (d, J = 8.4 Hz, 1H), 8.68
(s, 1H), 8.67 (s, 3H), 8.30−8.23 (m, 3H), 8.19−8.14 (m, 3H), 8.11 (d,
J = 5.6 Hz, 1H), 8.06 (d, J = 6.4 Hz, 1H), 7.99−7.88 (m, 6H), 7.85−
7.78 (m, 5H), 7.74 (dd, J = 5.6, 5.6 Hz, 1H), 7.63 (dd, J = 2.0, 6.0 Hz,
1H), 7.59 (dd, J = 6.0, 6.0 Hz, 1H), 7.41 (d, J = 8.0 Hz, 2H), 7.37 (d,
J = 8.0 Hz, 2H), 7.18−7.12 (m, 2H), 7.03 (dd, J = 7.6, 7.6 Hz, 2H),
6.91 (dd, J = 7.2, 7.2 Hz, 2H), 6.33 (dd, J = 7.6, 7.6 Hz, 2H), 2.57 (s,
3H), 2.56 (s, 6H), 2.55 (s, 3H). ESI−MS (in acetonitrile): m/z
−
−
863 ([M-2PF6 ]2+). HRMS (ESI−TOF): m/z [M-2PF6 ]2+ Anal.
Calcd for C83H58F6IrN6O2P2Re: 863.1601. Found: 863.1643.
Ir(CH−CH)Re2+. Ir(CC)Re2+ (10.0 mg, 4.96 μmol) and BIH
(45.0 mg, 201 μmol) were dissolved in an acetonitrile−pyridine−
CF3COOH mixed solution (4 mL, 3:1:0.1 v/v/v). After bubbling with
Ar for 30 min, the solution was irradiated with a Xe lamp equipped
with a band-pass filter (510 10 nm) for 8 h. The crude was purified
by ion-exchange chromatography (CM Sephadex C-25, eluent:
acetonitrile−water (1:1 v/v) containing NH4PF6 (0−8 mM)) and
silica-gel chromatography (eluent: CH2Cl2-MeOH (100:1 v/v)).
Obtained yellow solid was recrystallized with acetone/ether. The
yellow precipitate was filtered off and washed with ether. Yield: 6.6 mg
(66%). 1H NMR (400 MHz, acetone-d6): δ 8.86 (s, 1H), 8.70 (s, 1H),
8.41 (s, 1H), 8.40 (d, J = 7.6 Hz, 1H), 8.23 (d, J = 8.0 Hz, 2H), 8.19
(dd, J = 3.2, 6.0 Hz, 2H), 8.00−7.83 (m, 11H), 7.81 (dd, J = 3.2, 6.4
Hz, 2H), 7.60 (d, J = 5.6 Hz, 1H), 7.53 (d, J = 5.6 Hz, 1H), 7.35−7.32
(m, 12H), 7.10 (m, 12H), 7.02 (dd, J = 7.2, 7.2 Hz, 2H), 6.90 (dd, J =
7.2, 7.2 Hz, 2H), 6.34 (dd, J = 7.2, 7.2 Hz, 2H), 3.19 (m, 4H, −CH2−
CH2−), 2.60 (s, 3H, −CH3). 31P NMR (400 MHz, acetone-d6):
−
−
435 ([M-3PF6 ]3+), 725 ([M-2PF6 ]2+). HRMS (ESI−TOF): m/z
−
[M-3PF6 ]3+ Anal. Calcd for C68H54IrN10Ru: 435.1074. Found:
−
435.1057. [M-2PF6 ]2+ Anal. Calcd for C68H54F6IrN10PRu: 725.1432.
−
δ 20.9 (s, 2P, −PPh3), −143.6 (sep, 2P, 2PF6 ). FT-IR (in CH2Cl2)
νCO/cm−1: 1940, 1870. ESI−MS (in acetonitrile): m/z 864
Found: 725.1426.
Ru(CH2−CH2)Ir3+. Ru(CC)Ir3+ (5.8 mg, 3.3 μmol) and BIH (45 mg,
200 μmol) were dissolved in an acetonitrile−pyridine−CF3COOH
mixed solution (4 mL, 3:1:0.1 v/v/v). After bubbling with Ar for
30 min, the solution was irradiated with a Xe lamp equipped with a
band-pass filter (600 10 nm) for 14 h. The crude was purified by ion-
exchange chromatography (CM Sephadex C-25, eluent: acetonitrile−
water (1:1 v/v) containing NH4PF6 (0−8 mM)). Some portion of
acetonitrile was evaporated under reduced pressure. The red precipitate
was filtered off and washed with water and ether. Yield: 4.5 mg (78%).
1H NMR (400 MHz, acetone-d6): δ 8.81 (s, 1H), 8.79 (s, 1H), 8.76−
72 (m, 2H), 8.66 (s, 4H), 8.27−8.22 (m, 3H), 8.13 (dd, J = 8.0, 8.0 Hz,
1H), 8.08 (d, J = 5.2 Hz, 1H), 8.01 (d, J = 5.2 Hz, 1H), 7.98−7.87
(m, 6H), 7.83−7.74 (m, 6H), 7.69 (d, J = 6.4, 6.4 Hz, 1H), 7.61−7.48
(m, 3H), 7.40−7.34 (m, 2H), 7.29 (d, J = 7.2 Hz, 1H), 7.23 (d, J =
4.8 Hz, 1H), 7.17−7.08 (m, 2H), 7.02 (m, J = 7.2 Hz, 2H), 6.92−6.88
(m, 2H), 6.32 (d, J = 7.6 Hz, 2H), 3.29 (m, 4H, −CH2−CH2−), 2.56
(s, 6H), 2.54 (s, 3H), 2.52 (s, 3H). ESI−MS (in acetonitrile): m/z
−
−
([M-2PF6 ]2+). HRMS (ESI−TOF): m/z [M-2PF6 ]2+ Anal. Calcd
for C83H60F6IrN6O2P2Re: 864.1679. Found: 864.1676.
Ru(CC)Ru4+. [Ru(dmb)2(vbpy)](PF6)2 (22 mg, 23 μmol) and
Grubbs catalyst II (2.5 mg, 2.9 μmol) were dissolved in CH2Cl2
(ca. 10 mL degassed by N2). The solution was refluxed with N2
bubbling for 16 h (in dim light). Then Grubbs catalyst II (1.95 mg,
2.3 μmol) and CH2Cl2 (ca. 10 mL degassed under N2) were added
as the second charge and refluxed 17 h. Another Grubbs catalyst II
(2.5 mg, 2.9 μmol) and CH2Cl2 (ca. 10 mL degassed under N2) were
added as the third charge and refluxed for 6 h. The solvent was
removed in vacuo, and the black-red solid was collected. The solid
was purified by size exclusion chromatography, and the obtained red
solution was evaporated. The residue was dissolved in CH2Cl2 and
washed with water (containing NH4PF6) twice. After evaporating, the
obtained red solid was dissolved in MeOH, and a concentrated
methanol solution of NH4PF6 was added. Some water was added to
the solution, and the MeOH evaporated under reduced pressure.
After filtration, red solid was collected and washed with water and
Et2O and dried in a vacuum. Yield: 7.8 mg (38%). 1H NMR (400 MHz,
acetone-d6): δ 8.94 (s, 2H), 8.70 (s, 2H), 8.67 (s, 2H), 8.66 (s, 6H),
8.02 (d, J = 6.0 Hz, 2H), 7.90 (d, J = 6.8 Hz, 2H), 7.89 (s, 2H), 7.84−
7.81 (m, 8H), 7.67 (d, J = 6.0 Hz, 2H), 7.40−7.37 (m, 10H), 2.58
(s, 6H), 2.56 (s, 6H), 2.55 (s, 6H), 2.54 (s, 12H). ESI−MS
−
−
436 ([M-3PF6 ]3+), 726 ([M-2PF6 ]2+). HRMS (ESI−TOF): m/z
−
[M-3PF6 ]3+ Anal. Calcd for C68H58IrN10Ru: 436.4512. Found:
−
436.4529. [M-2PF6 ]2+ Anal. Calcd for C68H58F6IrN10PRu: 727.1589.
Found: 727.1597.
−
(in acetonitrile): m/z 326 ([M-4PF6 ]4+), 483 ([M-3PF6−]3+), 797
−
([M-2PF6−]2+). HRMS (ESI−TOF): m/z [M-4PF6 ]4+ Anal. Calcd for
C72H68N12Ru2: 326.0952. Found: 326.0920.
Ru(CH−CH)Ru4+. Ru(CC)Ru4+ (2.6 mg, 1.4 μmol) and BIH
(9.0 mg, 40 μmol) were dissolved in an acetonitrile−pyridine−
CF3COOH mixed solution (4 mL, 3:1:0.1 v/v/v). After bubbling with
Ar for 30 min, the solution was irradiated with a Xe lamp equipped
with band-pass filter (600
10 nm) for 15 h. The crude was
purified by ion-exchange chromatography (CM Sephadex C-25, eluent:
acetonitrile−water (1:1 v/v) containing NH4PF6 (0−16 mM)). Some
portion of acetonitrile was evaporated under reduced pressure. The red
precipitate was filtered off and washed with water and ether. Yield:
1
1.6 mg (62%). H NMR (400 MHz, acetone-d6): δ 8.78 (s, 1H), 8.75
(s, 1H), 8.65 (s, 10H), 7.89 (d, J = 5.6 Hz, 2H), 7.84−7.80 (m, 8H),
7.79 (d, J = 6.0 Hz, 1H), 7.74 (d, J = 5.2 Hz, 1H), 7.51 (d, J = 6.0 Hz,
1H), 7.50 (d, J = 6.0 Hz, 1H), 7.37 (d, J = 5.6 Hz, 8H), 7.33 (d, J =
5.6 Hz, 1H), 7.20 (d, J = 4.8 Hz, 1H), 3.20 (s, 4H, −CH2−CH2−),
Ru(CH−CH)Re(CH−CH)Ru5+. Ru(CC)Re(CC)Ru5+ (10.2 mg,
3.31 μmol) and BIH (45.0 mg, 201 μmol) were dissolved in an
L
Inorg. Chem. XXXX, XXX, XXX−XXX