New Journal of Chemistry
Page 8 of 11
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130.0 (s, CPh), 130.5 (s, CPh), 133.8 (s, CPh), 137.3 (s, ipso CPh), 143.3
2.51 (d, JHP = 15 Hz, 1H, =CCH2), 3.72 (d, JDHHO=I: 1102.1H03z9,/1CH9,NNJ0C1H222)0,F
(s, ipso CPh), 178.2 (s, C-Ru). 31P{1H} NMR (CDCl3): δP = -144.2 (septet, 4.18 (s, 1H, =CCH2), 4.36 (d, JHH = 8 Hz, 2H, NCH2), 4.82 (s, 2H,
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1JPF = 716 Hz, PF6), 57.2 (s, PPh3). CHN found (calcd) for
[C37H35F6N3O2P2Ru]×0.5H2O: C, 52.95 (52.92), H, 4.55 (4.32), N, 5.03
(5.00)%. HR-MS (ESI): m/z 686.1208 (3+) calcd for C37H35N3O2PRu
686.1510.
C5H4CH3), 5.00 (s, 2H, C5H4CH3), 6.81 (s, 1H, CimiH), 6.82 (s, 1H, CimiH),
6.82-7.00 (m, 5H, HPh), 7.14-7.45 (m, 15H, HPh). 13C{1H} NMR (CDCl3):
δC = 12.2 (s, C5H4CH3), 33.3 (s, CCH3), 53.3 (s, =CCH2), 56.9 (s, NCH2),
57.7 (s, NCH2), 78.3 (s, C5H4CH3), 80.3 (s, =CCH2), 87.9 (s, C5H4CH3),
101.5 (s, C5H4CH3), 121.2 (s, CimiH), 124.7 (s, CimiH), 128.1 (s, CPh),
128.8 (s, CPh), 129.0 (s, CPh), 129.2 (s, CPh), 130.8 (s, CPh), 133.5 (s,
CPh), 133.7 (s, ipso CPh), 135.8 (s, ipso CPh), 176.1 (s, C-Ru). 31P{1H}
NMR (CDCl3): δP = -144.2 (septet, 1JPF = 713 Hz, PF6), 58.1 (s, PPh3).
CHN found (calcd) for [C38H38F6N2P2Ru]×0.7CH2Cl2: C, 54.06 (54.23),
H, 4.51 (4.63), N, 3.49 (3.27)%. HR-MS (ESI): m/z 655.1816 (7+) calcd
for C38H38N2PRu 655.1816.
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[CpRu(PPh3)(L4)]PF6 (4): Yield: 55%. H NMR ((CD3)2CO): δH = 1.60
(d, 2JHH = 12 Hz, 1H, NCH2), 1.95 (s, 3H, CCH3), 2.15 (d, 3JHP = 15 Hz,
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1H, CH2), 3.07 (dddd, JHH = 6, 10, 14, 36 Hz, 2H, NCH2CH2), 3.67
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(dddd, JHH = 6, 10, 14, 77 Hz, 2H, NCH2CH2), 3.85 (d, JHH = 12 Hz,
1H, NCH2), 4.03 (s, 1H, =CH2), 5.27 (s, 5H, C5H5), 7.06 (s, 1H, CimiH),
7.08 (s, 1H, CimiH), 7.10-7.24 (m, 5H, HPh), 7.25-7.57 (m, 15H, HPh).
13C{1H} NMR (CDCl3): δC = 32.8 (s, CCH3), 48.3 (s, =CCH2), 50.9 (s,
NCH2CH2), 56.8 (s, NCH2), 65.8 (s, NCH2CH2), 82.4 (s, =CCH2), 87.5 (s,
C5H5), 121.3 (s, CimiH), 122.9 (s, CimiH), 128.4 (s, CPh), 128.8 (s, CPh),
129.0 (s, CPh), 130.5 (s, CPh), 131.4 (s, CPh), 133.4 (s, CPh), 133.9 (s,
ipso CPh), 137.0 (s, ipso CPh), 174.7 (s, C-Ru). 31P{1H} NMR (CDCl3): δP
= -144.2 (septet, 1JPF = 713 Hz, PF6), 57.4 (s, PPh3). CHN found (calcd)
for [C38H38F6N2P2Ru]×0.5CH2Cl2: C, 54.59 (54.91), H, 4.40 (4.67), N,
3.15 (3.33)%. HR-MS (ESI): m/z 655.1877 (4+) calcd for C38H38N2PRu
655.1816.
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[CpRu(AsPh3)(L2)]PF6 (8): Yield: 62%. H NMR (CDCl3): δH = 1.86 (s,
3H, CCH3), 2.08 (d, 2JHH = 12 Hz, 1H, NCH2), 2.15 (s, 1H, =CCH2), 3.73
(s, 1H, =CCH2), 3.80 (d, 2JHH = 12 Hz, 1H, NCH2), 4.43 (dd, 2JHH = 16,
48 Hz, 2H, NCH2), 4.81 (s, 5H, C5H5), 6.68 (s, 1H, CimiH), 6.70 (s, 1H,
CimiH), 6.85-7.05 (m, 5H, HPh), 7.18-7.41 (m, 15H, HPh). 13C{1H} NMR
(CDCl3): δC = 30.9 (s, CCH3), 46.0 (s, =CCH2), 57.3 (s, NCH2), 65.8 (s,
NCH2), 79.2.4 (s, =CCH2), 85.0 (s, C5H5), 121.0 (s, CimiH), 122.2 (s,
CimiH), 128.2 (s, CPh), 128.6 (s, CPh), 129.2 (s, CPh), 130.7 (s, CPh), 132.5
(s, CPh), 134.8 (s, CPh), 135.4 (s, ipso CPh), 139.4 (s, ipso CPh), 176.1 (s,
C-Ru). 31P{1H} NMR (CDCl3): δP = -144.2 (septet, 1JPF = 713 Hz, PF6).
CHN found (calcd) for [C37H36F6N2AsPRu]×0.5CH3CN: C, 53.35
(53.68), H, 4.58 (4.45), N, 4.24 (4.12)%. HR-MS (ESI): m/z 685.1140
(8+) calcd for C37H36N2AsRu 685.1140.
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[CpRu(PPh3)(L5)]PF6 (5): Yield: 61%. H NMR (CDCl3): δH = 1.53 (d,
2JHH = 12 Hz, 1H, NCH2), 1.54 (s, 3H, CCH3), 1.91 (s, 3H, CCH3), 2.07
(d, 3JHP = 15 Hz, 1H, =CCH2), 3.59 (m, 2H, NCH2), 3.69 (d, 2JHH = 12 Hz,
1H, NCH2), 3.85 (s, 1H, =CCH2), 4.50 (s, 1H, =CCH2), 4.98 (s, 1H,
=CCH2), 5.00 (s, 5H, C5H5), 7.08 (s, 1H, CimiH), 7.10 (s, 1H, CimiH),
7.37-7.67 (m, 15H, HPh). 13C{1H} NMR (CDCl3): δC = 30.9 (s, CCH3),
32.9 (s, CCH3), 48.9 (s, =CCH2), 55.0 (s, =CCH2), 57.0 (s, NCH2), 65.8
(s, NCH2), 79.9 (s, =CCH2), 82.5 (s, =CCH2), 87.6 (s, C5H5), 121.0 (s,
CimiH), 124.6 (s, CimiH), 128.4 (s, CPh), 130.8 (s, CPh), 131.9 (s, CPh),
140.8 (s, ipso CPh), 175.6 (s, C-Ru). 31P{1H} NMR (CDCl3): δP = -144.3
Synthesis of [CpRu(PPh3)(L1)]I3 (9): To a solution of complex 1 (0.36
g, 0.5 mmol) in CH2Cl2 (30 mL) was added I2 crystals (0.26 g, 1 mmol).
The resulting mixture was stirred upon which an immediate
darkening of the light yellow solution was observed. After 2 hours
reaction time, the mixture was concentrated in vacuo, extracted
with hexane (3 20 mL). The residue was taken up in CH2Cl2, passed
through a plug of silica, and cooled. Dark yellow crystals formed
overnight. Yield: 77%. 1H NMR ((CD3)2CO): δH = 1.13 (d, 2JHH = 12 Hz,
1H, NCH2), 1.74 (s, 3H, CCH3), 1.89 (d, 3JHP = 15 Hz, 1H, =CCH2), 2.93
(s, 3H, NCH3), 3.51 (d, 2JHH = 12 Hz, 1H, NCH2), 3.75 (s, 1H, =CCH2),
5.03 (s, 5H, C5H5), 6.91 (s, 1H, CimiH), 7.01 (s, 1H, CimiH), 7.22-7.47
(m, 15H, HPh). 13C{1H} NMR (CD3CN): δC = 32.7 (s, CCH3), 37.8 (s,
NCH3), 48.1 (s, =CCH2), 57.5 (s, NCH2), 81.1 (s, =CCH2), 88.8 (s, C5H5),
118.3 (s, CimiH), 121.4 (s, CimiH), 126.0 (s, CPh), 129.5 (s, CPh), 131.4
(s, CPh), 134.3 (s, ipso CPh), 175.8 (s, C-Ru). 31P{1H} NMR ((CD3)2CO):
δP = 58.1 (s, PPh3). HR-MS (ESI): m/z 565.1344 (1+) calcd for
C31H32N2PRu 565.1347.
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(septet, JPF = 713 Hz, PF6), 57.5 (s, PPh3). CHN found (calcd) for
[C34H36F6N2P2Ru]×0.25CH2Cl2: C, 53.70 (53.36), H, 4.59 (4.77), N,
3.63 (3.66)%. HR-MS (ESI): m/z 605.1715 (5+) calcd for C34H36N2PRu
605.1660.
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[CpRu(PPh3)(L6)]PF6 (6): Yield: 51%. H NMR (CDCl3): δH = 1.67 (d,
2JHH = 12 Hz, 1H, NCH2), 2.01 (s, 3H, CCH3), 2.23 (d, 3JHP = 15 Hz, 1H,
=CCH2), 4.00 (d, 2JHH = 12 Hz, 1H, NCH2), 4.07 (s, 1H, =CCH2), 4.67 (s,
2H, NCH2), 4.93 (s, 5H, C5H5), 7.21-7.24 (m, 4H, HPh), 7.34-7.37 (m,
4H, HPh), 7.41-7.46 (m, 12H, HPh), 7.52 (m, 2H, HPh), 7.61-7.66 (m,
3H, HPh). 13C{1H} NMR (CDCl3): δC = 30.9 (s, CCH3), 49.0 (s, =CCH2),
50.7 (s, NCH2), 54.4 (s, NCH2), 80.6 (s, =CCH2), 88.2 (s, C5H5), 125.0
(s, CimiH), 126.9 (s, CimiH), 128.0 (s, CimiH), 128.4 (s, CPh), 128.5 (s,
CimiH), 128.9 (s, CPh), 129.4 (s, CPh), 130.5 (s, CPh), 131.9 (s, CPh), 132.1
(s, CPh), 133.6 (s, ipso CPh), 133.7 (s, ipso CPh), 192.7 (s, C-Ru). 31P{1H}
NMR (CDCl3): δP = -144.2 (septet, 1JPF = 713 Hz, PF6), 56.5 (s, PPh3).
CHN found (calcd) for [C41H38F6N2P2Ru]×0.9CH2Cl2: C, 55.19 (55.26),
H, 4.25 (4.40), N, 2.95 (3.08)%. HR-MS (ESI): m/z 691.1312 (6+) calcd
for C41H38N2PRu 691.1816.
Transfer hydrogenation catalysis
To a round-bottom flask containing the carbonyl substrate (0.6
mmol), base (1.2 equivalents), anisole (65 μL, 0.6 mmol), and
ruthenium complex (2 mol%, 12 μmol) was added 2-propanol (4
mL) and the subsequent reaction mixture was heated under reflux
at 110°C for the time indicated. Aliquots (0.05 mL) diluted with
CDCl3 was analysed with 1H-NMR through which conversions were
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[MeCpRu(PPh3)(L2)]PF6 (7): Yield: 43%. H NMR (CDCl3): δH = 1.50
(d, 2JHH = 12 Hz, 1H, NCH2), 1.90 (s, 3H, CCH3), 1.94 (s, 3H, C5H4CH3),
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