Organometallics
Article
(d, J = 8.4 Hz, 2 H, Ha), 7.94 (dd, J = 8.4 and 7.4 Hz, 2 H, Hb), 7.82
(d, J = 6.0 Hz, 2 H, Hd), 7.72 (dd, J = 5.2 and 5.2 Hz, 2 H, Hm), 7.11
(ddd, J = 7.4, 6.0, 2.0 Hz, 2 H, Hc), 6.68 (ddd, JH−F = 9.6, 9.2 Hz,
4JH−H = 2.4 Hz, 2 H, Hh), 5.82 (dd, JH−F = 9.2 Hz, 4JH−H = 2.4 Hz, 2 H,
Hj). 13C{1H} NMR (100 MHz, CD3NO2, room temperature, δ/ppm):
166.4, 164.3 (dd, JCF = 209.0, 13.0 Hz, Ci), 165.2 (d, JCF = 7.0 Hz, Ce),
163.8, 161.7 (dd, JCF = 203.0, 13.0 Hz, Cg), 163.5 (Co), 161.6 (Cl),
159.6 (Cn), 153.3 (d, JCF = 7.0 Hz, Cf), 151.4 (Cd), 141.3 (Cb), 129.8
(Ck), 126.9 (Cm), 125.5 (Cc), 125.3 (Ca), 115.5 (d, JCF = 18.0 Hz, Cj),
100.5 (t, JCF = 27.0 Hz, Ch). ESI-MS: m/z 731 [M PF6]+. Anal. Calcd
for C30H18N6IrPF10: C, 41.15; H, 2.07; N, 9.60. Found: C, 40.84; H,
2.07; N, 9.49.
8.00−7.94 (m, 4 H, Hb and Hd), 7.86 (t, J = 5.6 Hz, 2 H, Hm),
7.27−7.10 (m, 6H, Hc and Hq), 6.80 (d, J = 7.6 Hz, 2 H, Hq), 6.71
(ddd, J = 12.2, 9.6, 2.4 Hz, 2 H, Hh), 5.82 (dd, J = 8.8, 2.4, Hz, 2 H,
Hj), 2.17 (s, 6 H, Ar-CH3). 13C NMR (400 MHz, CD3NO2, room
temperature, δ/ppm): 167.1 (Co), 166.3, 164.1 (Ci), 164.9 (Ce),
163.7, 161.5 (Cg), 158.7 (Cl), 158.6 (Cn), 152.2 (Cd), 150.0 (Cf),
141.7 (Cb), 139.0 (Cq), 138.2 (Cp), 133.5 (Cs), 130.2 (Cm), 129.9
(Cr), 129.7 (Ck), 125.6 (Ca), 125.4 (Cc), 115.6 (Cj), 101.1 (Ch), 21.1
(Ar-CH3). Anal. Calcd for C44H32F10IrN6PPt + CH3CN: C, 42.69; H,
2.73; N, 7.58. Found: C, 42.31; H, 2.87; N, 7.26.
Preparation of 2c.
Preparation of 2a.
In air, [Ir(dFppy)2(bpm)](PF6) (68.4 mg, 0.080 mmol) and
(DMSO)2Pt(C6H4-p-Cl)2 (50.0 mg, 0.095 mmol) were
dissolved in CH3CN (5 mL). The solution was stirred for
120 min at 55 °C, and the solvent was removed under reduced
pressure. The residue was washed with Et2O and n-pentane
several times and dried under vacuum. The product was
obtained as a black solid (90 mg, 87%).
In air, [Ir(dFppy)2(bpm)](PF6) (288.6 mg, 0.33 mmol) and
(DMSO)2PtPh2 (202.2 mg, 0.40 mmol) were dissolved in
CH3CN (10 mL). The solution was stirred for 120 min at
55 °C, and the solvent was removed under reduced pressure.
The residue was washed with Et2O and n-pentane several times
and dried under vacuum. The product was obtained as a black
solid (371.4 mg, 92%). Black crystals of [Ir(dFppy)2(bpm)-
PtPh2](PF6) suitable for crystallographic studies were grown
by diffusing Et2O vapors into a solution of the complex in
CH3CN.
1H NMR (400 MHz, CD3NO2, room temperature, δ/ppm) (signal
1
assigned by H−1H COSY): 8.86 (dd, J = 1.6 and 5.6 Hz, 2 H, Hn),
8.71 (dd, J = 1.6 and 5.6 Hz, 2 H, Hl), 8.37 (d, J = 8.8 Hz, 2 H, Ha),
7.98 (t, J = 3.6 Hz, 2 H, Hb), 7.95 (d, J = 7.6 Hz, 2 H, Hd), 7.87 (t, J =
5.6 Hz, 2 H, Hm), 7.32 (d, J = 7.6 Hz, 4 H, Hq), 7.20 (t, J = 8.8 Hz, 2
H, Hc), 6.99 (d, J = 7.6 Hz, 4 H, Hr), 6.71 (ddd, J = 2.0, 9.2, 11.2 Hz, 2
H, Hh), 5.81 (dd, J = 2.0, 8.4 Hz, 2 H, Hj). 13C NMR (400 MHz,
CD3NO2, room temperature, δ/ppm): 167.0 (Co), 166.4, 164.1 (Ci),
164.9 (Ce), 163.7, 161.7 (Cg), 159.1 (Cl), 158.7 (Cn), 152.2 (Cd),
149.8 (Cf), 141.8 (Cb), 140.3 (Cq), 130.2 (Cm), 130.0 (Ck), 129.8
(Cr), 125.7 (Ca), 125.5 (Cc), 115.6 (Cj), 101.2 (Ch). Anal. Calcd for
C42H26Cl2F10IrN6PPt: C, 38.99; H, 2.03; N, 6.50. Found: C, 38.49, H,
2.13; N, 6.58.
1H NMR (400 MHz, CD3NO2, room temperature, δ/ppm) (signal
assigned by 1H−1H COSY): 8.90 (dd, J = 1.8, 5.5 Hz, 2 H, Hn), 8.70
(dd, J = 1.7, 5.5 Hz, 2 H, Hl), 8.36 (d, J = 8.4 Hz, 2 H, Ha), 8.00−7.94
(m, 4 H, Hb, Hd), 7.86 (t, J = 5.4 Hz, 2 H, Hm), 7.34 (d, J = 6.8 Hz, 4
H, Hq), 7.16 (t, J = 6.6 Hz, 2 H, Hc), 6.96 (t, J = 7.2 Hz, 4H, Hr), 6.84
(t, J = 7.2 Hz, 2 H, Hs), 6.71 (ddd, J = 2.0, 9.2, 12.0 Hz, Hh), 5.82 (dd,
J = 2.2, 8.6 Hz, 2H, Hj). 13C NMR (400 MHz, CD3NO2, room
temperature, δ/ppm): 165.4 (Co), 164.6, 162.5 (Ci), 163.3 (Ce),
162.0, 159.9(Cg), 157.2 (Cl), 157.0 (Cn), 150.6 (Cd), 148.3 (Cf),
140.8 (Cp), 140.0 (Cb), 137.6 (Cq), 128.4 (Cm), 128.2 (Ck), 127.2
(Cr), 124.1 (Ca), 123.8 (Cc), 122.8 (Cs), 114.0 (Cj), 99.5 (Ch).
Preparation of 2b.
Preparation of 2d.
In air, [Ir(dFppy)2(bpm)](PF6) (152.5 mg, 0.17 mmol) and
(DMSO)2PtPh(C6H4-p-Me) (108.6 mg, 0.21 mmol) were dis-
solved in CH3CN (5 mL). The solution was stirred for 120 min
at 55 °C, and the solvent was removed under reduced pressure.
The residue was washed with Et2O and n-pentane several times
and dried under vacuum. The product was obtained as a black
solid (189.6 mg, 90%).
In air, [Ir(dFppy)2(bpm)](PF6) (68.4 mg, 0.078 mmol) and
(DMSO)2Pt(tol)2 (50.0 mg, 0.094 mmol) were dissolved in
CH3CN (5 mL). The solution was stirred for 120 min at 55 °C,
and the solvent was removed under reduced pressure. The
residue was washed with Et2O and n-pentane several times and
dried under vacuum. The product was obtained as a black solid
(78.7 mg, 91%). Black crystals of [Ir(dFppy)2(bpm)Pt(tol)2]-
(PF6) suitable for crystallographic studies were grown by
diffusing Et2O vapors into a solution of the complex in CH3CN.
1H NMR (400 MHz, CD3NO2, room temperature, δ/ppm) (signal
1H NMR (400 MHz, CD3NO2, room temperature, δ/ppm) (signal
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assigned by H−1H COSY): 8.970−8.893 (m, 2 H, Hn, Hn′), 8.71
(ddd, J = 0.8, 1.6, 5.6 Hz, 2 H, Hl), 8.36 (d, J = 8.8 Hz, 2 H, Ha), 7.98
(t, J = 7.6 Hz, 2 H, Hb), 7.95 (d, J = 5.6 Hz, 2 H, Hd), 7.87−7.86 (m,
2 H, Hm), 7.33 (t, J = 7.2 Hz, 2 H, Hu), 7.21−7.14 (m, 4 H, Hc and
Hq), 6.983−6.94 (m, 2 H, Hv), 6.85−6.79 (m, 2 H, Hu and Hw), 6.71
(ddd, J = 2.4, 9.6, 12.4 Hz, 2 H, Hh), 5.8 2(dd, J = 2.4 and 8.8 Hz, 2 H,
Hj), 2.17 (s, 3 H, Ar-CH3). 13C NMR (400 MHz, CD3NO2, room
1
assigned by H−1H COSY): 8.96 (dd, J = 1.6 and 5.6 Hz, 2 H, Hn),
8.71 (dd, J = 1.6 and 5.6 Hz, 2 H, Hl), 8.36 (d, J = 8.4 Hz, 2 H, Ha),
H
Organometallics XXXX, XXX, XXX−XXX