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2H), 1.26 (m, 2H), 1.22 (m, 2H, CH2) ppm. 13C NMR (101
MHz, CDCl3) δ 93.53 (CpC), 92.25 (CpC), 84.75 (CpC), 84.04
(CpC), 34.9, 32.05, 31.72, 28.14, 26.93, 21.41, 10.44,
9.74 ppm.
4H, 2CH2), 1.16 (m, 4H), 0.91 (t, 3H, CH3) ppm. 13C NMR
(101 MHz, CDCl3) δ 88.7 (CpC), 88.5 (CpC), 84.2 (CpC), 51.56
(CH), 49.65 (CH), 32.88 (CH2), 30.77 (CH2), 30.59 (CH2), 29.69
(CH2), 29.50 (CH2), 29.28 (CH2), 29.07 (CH2), 26.81 (CH2),
26.44 (CH2), 25.44 (CH2), 25.17 (CH2), 24.12 (CH2), 15.18
(CH3) ppm.
Synthesis of ij(η5-C4Me4C8H17)IrIJcis-1,2-diaminocyclohexane)
Cl]Cl (4-Ir). Following the general procedure, 50.0 mg
(0.056 mmol) of ijCp*IJoctyl)IrCl2]2 was combined with
24.3 mg (0.212 mmol) of cis-1,2-diaminocyclohexane. Yield:
53.1 mg (0.092 mmol) (83%). HRMS/ESI+ (m/z): calcd. for
C23H43N2ij193Ir]Cl 575.2751; found 575.2764. Anal calc.
C23H43Cl2N2Ir C: 45.23, H: 7.10; found C: 45.19, H: 7.15. 1H
NMR (400 MHz, CDCl3) δ 3.38 (2, H), 3.10 (m, 2H), 2.24 (t,
J = 8.0 Hz, 4H), 2.08 (m, 2H), 1.84 (s, CpMe), 1.81 (s,
CpMe), 1.78 (s, CpMe), 1.76 (s, CpMe) 1.64 (t, J = 8.0 Hz,
2H, CH2), 1.43 (p, J = 8.1 Hz, 4H), 1.32 (m, 4H, 2CH2), 1.16
(m, 4H), 0.86 (t, 3H, CH3) ppm. 13C NMR (101 MHz, CDCl3)
δ 88.2 (CpC), 86.2 (CpC). 86.1 (CpC), 51.39 (CH), 49.34
(CH), 31.88 (CH2), 31.87 (CH2), 30.59 (CH2), 29.69 (CH2),
29.50 (CH2), 29.28 (CH2), 29.07 (CH2), 27.61 (CH2), 26.44
(CH2), 26.22 (CH2), 25.17 (CH2), 24.12 (CH2), 15.25 (CH3)
ppm.
Synthesis of ij(η5-C4Me4C12H25)IrIJcis-1,2-diaminocyclohexane)
Cl]Cl (8-Ir). Following the general procedure, 50.0 mg (0.051
mmol) of ijCp*IJdodecyl)IrCl2]2 was combined with 12.0 (0.105
mmol) mg of cis-1,2-diaminocyclohexane. Yield: 39.2 mg (0.062
mmol) (60%). HRMS/ESI+ (m/z): calcd. for C27H51N2ij193Ir]Cl
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631.3448 ; found 631.3475. H NMR (400 MHz, CDCl3) δ 5.69
(s, 1H, NH), 4.24 (s, 1H, NH), 3.24 (m. 1H, CH), 3.05 (m, 1H,
CH), 2.39–2.19 (bm, 6H), 1.85 (s, 15H, CpMe), 1.71–1.62 (m,
4H), 1.61–1.52 (m, 4H), 1.51–1.45 (m, 4H), 1.40 (m, 6H),
1.35–1.15 (m, 10H), 0.84 (m, 3H, CH3) ppm.
Synthesis of ij(η5-C5Me5)IrIJN,N,N′,N′-tetramethyl)ethylenediamine)
Cl]Cl (9-Ir). Following the general procedure, 50.0 mg (0.062
mmol) of ijCp*IrCl2]2 was combined in dichloromethane with
18.1 mg (0.155 mmol) of N,N,N′,N′-tetramethylethylenediamine.
Yield: 42.2 mg (0.088 mmol). HRMS/ESI+ (m/z): calcd. for
C16H31N2ij193Ir]Cl 479.1805; found 479.1804. 1H NMR
(400 MHz, CDCl3) δ 3.62 (m, 3H, CH3), 3.23 (s, 3H, CH3), 2.88
(m, 3H, CH3), 2.42 (m, 2H, CH2) 1.89 (s, 15H, CpMe) ppm.
Synthesis of ij(η5-C5Me5)IrIJN,N,N′-trimethyl)ethylenediamine)
Cl]Cl (10-Ir). Following the general procedure, 50.0 mg (0.062
mmol) of ijCp*IrCl2]2 was combined in dichloromethane with
17.8 mg (0.174 mmol) of N,N,N′-trimethylethylenediamine
dissolved in 10 mL of methanol. Yield: 36.2 mg (0.078 mmol).
HRMS/ESI+ (m/z): calcd. for C15H29N2ij193Ir]Cl 465.1648; found
465.1650. 1H NMR (400 MHz, CDCl3) δ 4.65 (br s, 1H, NH), 3.42
(m, 3H, CH3), 3.12 (m, 2H, CH2), 2.65 (m, 3H, CH3), 1.87 (s,
15H, CpMe) ppm.
Synthesis of ij(η5-C4Me4C6H13)IrIJcis-1,2-diaminocyclohexane)
Cl]Cl (5-Ir). Following the general procedure, 50 mg (0.057
mmol) of ijIrCp*IJhexyl)Cl2]2 was combined with 15.9 mg (0.139
mmol) of cis-1,2-diaminocyclohexane. Yield: 52.0 mg (0.095
mmol) (85%).HRMS/ESI+ (m/z): calcd. for C21H39N2ij193Ir]Cl
547.2509; found 547.2541. Anal calc. C: 43.29, H: 6.75; found
C: 43.078, H: 6.74. 1H NMR (400 MHz, CDCl3) δ 6.51 (s, 1H,
NH), 5.71 (s, 1H, NH), 4.03 (m, 1H, CH), 3.31 (m, 1H, CH),
2.24 (t, J = 8.5, 2H), 1.89–1.81 (2s, 15H, CpMe), 1.78 (m, 4H),
1.47–1.34 (m, 4H), 1.34–1.12 (m, 2H), 0.92–0.76 (m, 3H, CH3)
ppm. 13C NMR (101 MHz, CDCl3) δ 87.41 (CpC), 86.14 (CpC),
47.6 (CH), 46.31 (CH), 35.55 (CH2), 32.64 (CH2), 29.69 (CH2),
29.50 (CH2), 27.61 (CH2), 26.44 (CH2), 26.22, 24.12 (CH2),
12.45 (CH3), 10.4 (CpMe) ppm.
Synthesis of ij(η5-C5Me5)IrIJN-IJ1-benzyl)ethylenediamine)
Cl]ijCl] (11-Ir). Following the general procedure: 50.0 mg
(0.062 mmol) of ijCp*IrCl2]2 was combined in dichloromethane
with 19.8 mg (0.171 mmol) of N-IJ1-benzyl)ethylenediamine
dissolved in 10 mL of methanol. Yield: 42.3 mg (0.082
mmol). HRMS/ESI+ (m/z): calcd. for C19H29N2ij193Ir]Cl
513.1649; found 513.1648. 1H NMR (400 MHz, CDCl3) δ 7.39
(m, 4H, CH), 7.26 (d, 1H, CH), 5.68 (d, 2H, NH), 5.52 (s, 1H,
NH), 4.57 (s, 2H), 2.1 (br s, 2H), 1.73 (s, 15H, CpMe), 1.35 (s,
2H) ppm. 13C NMR (101 MHz, CDCl3) δ 125.6 (aryl), 124.9
(aryl), 88.2 (CpC), 87.1 (CpC), 55.2 (CH2), 51.4 (CH2), 12.5
(CH3) ppm.
Synthesis of ij(η5-C5Me5)IrIJ -trans-1,2-diaminocyclohexane)
Cl]Cl (6-Ir). Following the general procedure, 47.1 mg (0.059
mmol) of ijCp*IrCl2]2 was combined with 15.2 mg (0.133
mmol) of trans-1,2-diaminocyclohexane. Yield 48.1 mg (0.101
mmol) (81%). Calcd. for C16H29N2ij193Ir]Cl 477.1765; found
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477.1761. H NMR (400 MHz, CDCl3) δ 5.68 (s, 2H, NH2) 3.27
(m, 1H, CH), 3.15 (m, 1H, CH), 2.25 (m, 2H), 2.08 (d, J = 11.6
Hz, 2H), 1.84 (2s, 15H, CpMe), 1.65 (q, J = 11.6 Hz, 2H, CH2),
1.43 (q, J = 12.9 Hz, 2H) 1.26 (m, 2H), 1.22 (m, 2H, CH2)
ppm. 13C NMR (101 MHz, CDCl3) δ 94.85 (CpC), 93.25 (CpC),
84.75 (CpC), 84.04 (CpC), 34.9, 32.05, 30.82, 28.14, 27.33,
21.41, (cyclohexane) 10.18 (CpMe) ppm.
Synthesis of ij(η5-C5Me4C8H17)IrIJN-IJ1-naphthyl)ethylenediamine)
Cl]Cl (12-Ir). Following the general procedure, 50.0 mg (0.056
mmol) of ijCp*IJoctyl)IrCl2]2 was combined in dichloromethane
with 32.1 mg (0.171 mmol) of N-IJ1-napthyl)ethylenediamine
dissolved in 10 mL of methanol. Yield: 40.6 mg (0.062 mmol)
(55%). HRMS/ESI+ (m/z): calcd. for C29H43N2ij193Ir] 647.2321;
found 647.2394. Anal calc. C29H43Cl2N2Ir C: 49.71, H: 6.46;
Synthesis of ij(η5-C4Me4C8H17)IrIJtrans- -1,2-diaminocyclohexane)
Cl]Cl (7-Ir). Following the general procedure, 75.0 mg (0.083
mmol) of ijCp*IJoctyl)IrCl2]2 was combined with 36.4 mg (0.318
mmol) of trans-1,2-diaminocyclohexane. Yield: 71.0 mg (0.119
mmol) (65%). HRMS/ESI+ (m/z): calcd for C23H43N2ij193Ir]Cl
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575.2755; found 575.2771. H NMR (400 MHz, CDCl3) δ 3.56
found C: 48.86, H: 5.96. H NMR (400 MHz, CDCl3) δ 7.55 (d,
(2, NH2), 3.36 (m, 2H), 2.75 (t, J = 9.5 Hz, 4H), 2.17 (m, 2H),
1.86 (s, CpMe), 1.84 (s, CpMe), 1.81 (s, CpMe), 1.76 (s, CpMe),
1.64 (t, J = 9.5 Hz, 2H, CH2), 1.43 (p, J = 8.1 Hz, 4H), 1.37 (m,
J = 6.9 Hz, 1H, ArH), 7.41 (d, J = 6.9 Hz, 1H, ArH), 7.14 (m,
4H, ArH), 4.88 (m, 2H), 3.72 (d, J = 7.5 Hz, 1H), 3.60 (d, J =
7.5 Hz, 1H), 3.11 (s, 2H), 2.36 (t, J = 11.5 Hz, 2H), 2.02 (s, 3H,
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Med. Chem. Commun.