E. de Julián et al.
MolecularCatalysis456(2018)75–86
298 K): δ = 12.07 (s, 1H, NH), 8.59 (s, 1H, CH C4H6N2), 7.65 (d,
JHH = 8.8 Hz, 2H, H3,5 C5H3N), 7.49 (t, JHH = 8.8 Hz, 1H, H4 C5H3N),
6.38 (s, 1H, CH C4H6N2), 4.80 (pt, JHH = 8.8 Hz, 2H, OCH2), 4.67 (pt,
JHH = 8.8 Hz, 2H, OCH2), 4.04 (m, 2H, CHiPr), 2.36 (s, 3H, CH3), 1.71
(m, 2H, CHMe2), 0.79 (d, JHH = 7.2 Hz, 6H, CHMe2), 0.78 (d, JHH
= 6.8 Hz, 6H, CHMe2) ppm. 13C{1H} NMR (100.62 MHz, CDCl3, 298 K):
δ = 166.5 (s, OCN), 152.6 (s, C2,6 C5H3N), 143.3 (s, CH C4H6N2), 139.8
(s, CCH3), 127.1 (s, C4 C5H3N), 122.9 (s, C3,5 C5H3N), 106.3 (s, CH
C4H6N2), 71.4 (s, OCH2), 69.7 (s, CHiPr), 29.1 (s, CHMe2), 19.4, 15.6
(2 s, CHMe2), 11.2 (s, CH3) ppm.
CHPh), 4.56 (m, 2H, OCH2) ppm. 13C{1H} NMR (100.62 MHz, CDCl3,
298 K): δ = 168.0 (s, OCN), 158.6 (s, CH C9H7N), 152.0 (s, C2,6 C5H3N),
147.5, 137.6 (2s, CH C9H7N), 134.3, 130.4 (2s, C C9H7N), 128.2-127.5
(CH C9H7N, C4 C5H3N, Ph), 126.2, 125.6 (2s, CH C9H7N), 123.4, 123.3
(2s, C3,5 C5H3N), 118.6 (s, CH C9H7N), 78.5, 78.4 (2s, OCH2), 69.1 (s,
CHPh) ppm.
Complex 6b: Yield 81% (25 mg, 0.040 mmol). Color: dark purple.
Anal. Calc. for C27H23Cl2N5O2Ru (621.48): C, 52.18; H, 3.73; N, 11.27.
Found: C, 52.66; H, 4.10; N, 10.71. 1H NMR (400.13 MHz, CDCl3,
298 K): δ = 8.69 (s, 2H, C4H4N2), 7.82 (d, JHH = 7.8 Hz, 2H, H3,5
C5H3N), 7.74 (s, 2H, C4H4N2), 7.66 (t, JHH = 7.8 Hz, 1H, H4 C5H3N),
7.23-7.14 (m, 10H, Ph), 5.25 (dd, JHH = 11.2 Hz, JHH = 8.8 Hz, 2H,
OCH2), 5.08 (pt, JHH = 11.2 Hz, 2H, CHPh), 4.60 (dd, JHH = 11.2 Hz,
JHH = 8.8 Hz, 2H, OCH2) ppm. 13C{1H} NMR (100.62 MHz, CDCl3,
298 K): δ = 167.5 (s, OCN), 151.3 (s, C2,6 C5H3N), 149.9 (s, C4H4N2),
143.0 (s, C4H4N2), 137.1 (s, Cipso Ph), 129.2 (s, C4 C5H3N), 128.6 (s,
Ph), 123.3 (s, C3,5 C5H3N), 78.4 (s, OCH2), 69.3 (s, CHPh) ppm.
Complex 7b: Yield 77% (24 mg, 0.039 mmol). Color: dark purple.
Anal. Calc. for C27H25Cl2N5O2Ru (623.50): C, 52.01; H, 4.04; N, 11.23.
Found: C, 51.66; H, 4.16; N, 11.06. 1H NMR (400.13 MHz, CDCl3,
298 K): δ = 7.74 (d, JHH = 7.8 Hz, 2H, H3,5 C5H3N), 7.50 (t, JHH
= 7.8 Hz, 1H, H4 C5H3N), 7.22 (m, 10H, Ph), 6.97 (s, 1H, NCHCHN),
6.80 (s, 1H, NCHCHN), 6.34 (s, 1H, NCHN), 5.21 (pt, JHH = 10.9 Hz,
2H, OCH2), 5.00 (pt, JHH = 10.9 Hz, 2H, CHPh), 4.57 (pt,
JHH = 10.9 Hz, 2H, OCH2), 3.31 (s, 3H, NCH3) ppm. 13C{1H} NMR
(100.62 MHz, CDCl3, 298 K): δ = 168.2 (s, OCN), 152.3 (s, C2,6 C5H3N),
140.7 (s, NCHCHN), 138.3 (s, Cipso Ph), 132.1 (s, NCHCHN), 128.7,
128.1, 127.7 (3 s, Ph), 125.5 (s, C4 C5H3N), 123.3 (s, C3,5 C5H3N), 118.0
(s, NCHN), 78.4 (s, OCH2), 69.0 (s, CHPh), 33.7 (s, NCH3) ppm.
Complex 8b: Yield 75% (26 mg, 0.038 mmol). Color: dark purple.
Anal. Calc. for C33H29Cl2N5O2Ru (699.60): C, 56.66; H, 4.18; N, 10.01.
Found: C, 56.65; H, 4.39; N, 10.14. 1H NMR (400.13 MHz, CD2Cl2,
298 K): δ = 7.82 (d, JHH = 7.6 Hz, 2H, H3,5 C5H3N), 7.55 (m, 1H, H4
C5H3N), 7.42-7.05 (m, 16H, Ph, NCHCHN), 6.96 (s, 1H, NCHCHN),
6.42 (s, 1H, NCHN), 5.27 (pt, JHH = 9.2 Hz, 2H, OCH2), 5.15 (s, 1H,
NCH2), 5.06 (m, 2H, CHPh), 4.79 (s, 1H, NCH2), 4.57 (pt, JHH = 9.2 Hz,
2H, OCH2) ppm. 13C{1H} NMR (100.62 MHz, CD2Cl2, 298 K): δ = 168.1
(s, OCN), 152.2 (s, C2,6 C5H3N), 140.1 (s, NCHCHN), 138.4 (s, Cipso Ph),
132.0 (s, NCHCHN), 128.9-127.2 (Ph), 125.1 (s, C4 C5H3N), 122.9 (s,
C3,5 C5H3N), 117.4 (s, NCHN), 78.5 (s, OCH2), 68.9 (s, CHPh), 50.9 (s,
NCH2) ppm.
Complex 9b: Yield 76% (23 mg, 0.038 mmol). Color: dark pink.
Anal. Calc. for C26H23Cl2N5O2Ru (609.47): C, 51.24; H, 3.80; N, 11.49.
Found: C, 51.19; H, 3.69; N, 11.36. 1H NMR (400.13 MHz, CDCl3,
298 K): δ = 10.89 (s, 1H, NH), 7.78 (d, JHH = 8.0 Hz, 2H, H3,5 C5H3N),
7.57 (t, JHH = 8.0 Hz, 1H, H4 C5H3N), 7.47 (s, 1H, CH C3H4N2), 7.18
(m, 6H, Ph), 7.10 (m, 4H, Ph), 7.00 (s, 1H, CH C3H4N2), 5.94 (s, 1H, CH
C3H4N2), 5.22 (pt, JHH = 9.6 Hz, 2H, OCH2), 4.95 (pt, JHH = 9.6 Hz,
2H, CHPh), 4.64 (pt, JHH = 9.6 Hz, 2H, OCH2) ppm. 13C{1H} NMR
(100.62 MHz, CDCl3, 298 K): δ = 167.6 (s, OCN), 152.5 (s, C2,6 C5H3N),
141.6 (s, C3H4N2), 137.4 (s, Cipso Ph), 128.5, 128.2, 127.9 (3 s, Ph),
127.7 (s, C3H4N2), 127.0 (s, C4 C5H3N), 123.2 (s, C3,5 C5H3N), 105.2 (s,
CH C3H4N2), 78.4 (s, OCH2), 69.0 (s, CHPh) ppm.
Complex 10b: Yield 80% (25 mg, 0.040 mmol). Color: dark pink.
Anal. Calc. for C27H25Cl2N5O2Ru·0.5Et2O (660.56): C, 52.73; H, 4.58;
N, 10.60. Found: C, 52.43; H, 5.03; N, 10.79. 1H NMR (400.13 MHz,
CDCl3, 298 K): δ = 10.41 (s, 1H, NH), 7.77 (d, JHH = 7.6 Hz, 2H, H3,5
C5H3N), 7.55 (m, 1H, H4 C5H3N), 7.24-6.93 (m, 11H, CH C4H6N2, Ph),
5.65 (s, 1H, CH C4H6N2), 5.22 (pt, JHH = 10.0 Hz, 2H, OCH2), 5.12 (pt,
JHH = 10.0 Hz, 1H, CHPh), 4.96 (pt, JHH = 10.0 Hz, 1H, CHPh), 4.64
(pt, JHH = 10.0 Hz, 2H, OCH2), 1.97 (s, 3H, CH3) ppm. 13C{1H} NMR
(100.62 MHz, CDCl3, 298 K): δ = 167.7 (s, OCN), 152.7 (s, C2,6 C5H3N),
142.6 (s, CH C4H6N2), 137.9, 137.6 (2s, CCH3, Cipso Ph), 128.6-127.8
(Ph), 126.8 (s, C4 C5H3N), 123.3 (s, C3,5 C5H3N), 104.8 (s, CH C4H6N2),
78.4 (s, OCH2), 69.0 (s, CHPh), 10.8 (s, CH3) ppm.
Complex 11a: Yield 95% (31 mg, 0.057 mmol). Color: dark pink.
Exact mass for
C19H26Cl2N6O2Ru (542.05). MS-ESI: m/z = 542.1
([RuCl2(C2H3N3)(iPr-pybox)]+, 100%). 1H NMR (400.13 MHz, CDCl3,
298 K): δ = 13.53 (s, 1H, NH), 9.24 (s, 1H, C2H3N3), 8.65 (s, 1H,
C2H3N3), 7.69 (m, 2H, H3,5 C5H3N), 7.49 (m, 1H, H4 C5H3N), 4.83 (m,
2H, OCH2), 4.69 (m, 2H, OCH2), 4.05 (m, 2H, CHiPr), 1.60 (m, 2H,
CHMe2), 0.82 (m, 12H, CHMe2) ppm. 13C{1H} NMR (100.62 MHz,
CDCl3, 298 K): δ = 166.6 (s, OCN), 154.4 (s, C2H3N3), 152.0 (s, C2,6
C5H3N), 143.5 (s, C2H3N3), 128.2 (s, C4 C5H3N), 123.2 (s, C3,5 C5H3N),
71.6 (s, OCH2), 69.9 (s, CHiPr), 29.5 (s, CHMe2), 19.5, 15.6 (2 s,
CHMe2) ppm.
4.3. Synthesis of the complexes trans-[RuCl2(L){(R,R)-Ph-pybox}]
(L = pyridine (3b), 3-bromopyridine (4b), isoquinoline (5b), pyrazine
(6b), 1-methylimidazole (7b), 1-benzylimidazole (8b), pyrazole (9b), 3-
methylpyrazole (10b), 1H-1,2,4-triazole (11b))
A solution of complex trans-[RuCl2(η2-C2H4){(R,R)-Ph-pybox)] (1b)
(0.030 g, 0.05 mmol) and the N-donor ligand (0.10 mmol) in di-
chloromethane (10 mL) was heated at 55 °C in a sealed tube for 5.5 h.
The solution was transferred to a Schlenk and the solvent was then
removed under vacuum. The addition of diethyl ether (25 mL) pro-
duced the precipitation of the corresponding complex. The solvent was
decanted and the solid was washed with diethyl ether (3 x 5 mL) and
vacuum-dried.
Complex 3b: Yield 81% (25 mg, 0.040 mmol). Color: dark purple.
Anal. Calc. for C28H24Cl2N4O2Ru (620.50): C, 54.20; H, 3.90; N, 9.03.
Found: C, 54.22; H, 4.05; N, 8.79. 1H NMR (400.13 MHz, CDCl3, 298 K):
δ = 8.69 (d, JHH = 6.8 Hz, 2H, C5H5N), 7.79 (d, JHH = 8.4 Hz, 2H, H3,5
C5H3N), 7.60 (t, JHH = 8.4 Hz, 1H, H4 C5H3N), 7.25 (t, JHH = 8.4 Hz,
1H, C5H5N), 7.18-7.15 (m, 10H, Ph), 6.58 (dd, JHH = 8.4 Hz, JHH
= 6.8 Hz, 2H, C5H5N), 5.24 (pt, JHH = 8.4 Hz, 2H, OCH2), 5.14 (pt,
JHH = 8.4 Hz, 2H, CHPh), 4.56 (pt, JHH = 8.4 Hz, 2H, OCH2) ppm.
13C{1H} NMR (100.62 MHz, CDCl3, 298 K): δ = 168.1 (s, OCN), 155.1
(s, CH C5H5N), 152.1 (s, C2,6 C5H3N), 137.6 (s, Cipso Ph), 134.1 (s,
C5H5N), 128.3-128.1 (Ph), 127.6 (s, C4 C5H3N), 123.4 (s, C3,5 C5H3N),
122.2 (s, C5H5N), 78.4 (s, OCH2), 69.1 (s, CHPh) ppm.
Complex 4b: Yield 62% (22 mg, 0.031 mmol). Color: dark purple.
Anal. Calc. for C28H23Cl2N4O2BrRu (699.39): C, 48.09; H, 3.31; N, 8.01.
Found: C, 48.49; H, 3.40; N, 7.93. 1H NMR (400.13 MHz, CDCl3, 298 K):
δ = 8.97 (s, 1H, Br-C5H4N), 8.93 (d, JHH = 4.0 Hz, 1H, Br-C5H4N), 7.80
(d, JHH = 7.6 Hz, 2H, H3,5 C5H3N), 7.61 (t, JHH = 7.6 Hz, 1H, H4
C5H3N), 7.38 (m, 1H, Br-C5H4N), 6.94 (m, 10H, Ph), 6.45 (m, 1H, Br-
C5H4N), 5.29 (m, 2H, OCH2), 5.17 (m, 2H, CHPh), 4.55 (m, 2H, OCH2)
ppm. 13C{1H} NMR (100.62 MHz, CDCl3, 298 K): δ = 167.9 (s, OCN),
155.7 (s, CH Br-C5H4N), 153.4 (s, CH Br-C5H4N), 152.0 (s, C2,6 C5H3N),
137.4 (Cipso Ph), 137.1 (s, CH Br-C5H4N), 128.3 (br s, C4 C5H3N, Ph),
123.3 (s, C3,5 C5H3N), 122.8 (s, CH Br-C5H4N), 119.4 (s, C Br-C5H4N),
78.4 (s, OCH2), 69.1 (s, CHPh) ppm.
Complex 5b: Yield 58% (19 mg, 0.029 mmol). Color: dark purple.
Anal. Calc. for C32H26Cl2N4O2Ru (670.56): C, 57.32; H, 3.91; N, 8.36.
Found: C, 57.33; H, 3.92; N, 7.98. MS-ESI: m/z = 670.10
([RuCl2(C9H7N)(Ph-pybox)]+, 100%). 1H NMR (400.13 MHz, CDCl3,
298 K): δ = 9.31 (m, 1H, C9H7N), 8.58 (m, 1H, C9H7N), 7.99 (d,
JHH = 7.2 Hz, 2H, H3,5 C5H3N), 7.83 (m, 3H, H4 C5H3N, Ph), 7.73-7.59
(m, 13H, C9H7N, Ph), 5.38-5.21 (m, 3H, OCH2, CHPh), 5.14 (m, 1H,
Complex 11b: Yield 83% (25 mg, 0.042 mmol). Color: dark pink.
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