R. Müller, E. Hübner, N. Burzlaff
FULL PAPER
PPh3), 141.6 (C5Ј), 143.1 (C5), 155.2 (d, JC,P ϭ 2.7 Hz, C3), 158.3 3 H, C5ЈϪCH3), 5.80 (s, 1 H, HpzЈ), 5.93 (s, 1 H, Hpz), 6.45 (s, 1 H,
(C3Ј), 168.1 (CO2Ϫ), 189.0 (CO2Ϫ) ppm. 31P NMR (CDCl3, CH), 7.20 (m, 6 H, m-PPh3), 7.26 (m, 3 H, p-PPh3), 7.32 (m, 6 H,
161.8 MHz): δ ϭ 62.0 ppm. IR (THF): ν˜ ϭ 1674 vs (CO2Ϫ), 1653 o-PPh3), 7.33 (m, 2 H, m-Ph), 7.52 (t, 1 H, p-Ph), 8.33 (d, 2 H, o-
w, 1560 w (CϭN), 1464 m, 1436 m, 1420 w cmϪ1. IR (CH2Cl2): Ph) ppm. 13C NMR (CDCl3, 150.9 MHz): δ ϭ 11.1 (C5ϪCH3),
3
ν˜ ϭ 1661 vs (CO2Ϫ), 1563 w (CϭN), 1483 w, 1463 m, 1435 m, 1418
11.6 (C5ЈϪCH3), 13.4 (C3ϪCH3), 14.3 (C3ЈϪCH3), 69.0 (CH),
3
w cmϪ1. IR (KBr): ν˜ ϭ 1668 vs (CO2Ϫ), 1585 w, 1563 m (CϭN), 108.8 (C4Ј), 109.2 (C4), 128.2 (d, JC,P ϭ 11.6 Hz, m-PPh3), 128.3
1482 w, 1462 m, 1434 m, 1418 w cmϪ1. UV/Vis (CH2Cl2): λmax. (m-Ph), 129.6 (p-PPh3), 130.4 (o-Ph), 133.5 (i-Ph), 134.1 (d, 2JC,P ϭ
(log ε) ϭ 233.0 (4.37) nm. EI-MS (70 eV, 370 °C): m/z (%) ϭ 670
6.9 Hz, o-PPh3), 134.4 (p-Ph), 140.9 (C5), 142.9 (C5Ј), 154.6 (C3),
(3) [Mϩ], 626, (1) [Mϩ Ϫ CO2], 566 (3) [Mϩ Ϫ CO2 Ϫ HOAc]. 158.8 (C3Ј), 168.0 (CO2Ϫ), 169.7 (CO2Ϫ), 202.8 (CϭO) ppm. 31P
FAB-MS (NBOH): m/z (%) ϭ 748 (83) [Mϩ ϩ H2O ϩ HOAc], 670 NMR (CDCl3, 161.8 MHz): δ ϭ 57.9 ppm. IR (CH2Cl2): ν˜ ϭ 1659
(100) [Mϩ], 611 (39) [Mϩ Ϫ OAc], 566 (44) [Mϩ Ϫ CO2 Ϫ HOAc]. s, 1653 vs (CO2Ϫ), 1563 (CϭN), 1483 w, 1463 w, 1446 w, 1435 w,
C32H33N4O4PRu (669.68): calcd. C 57.39, H 4.97, N 8.37; found C 1418 w cmϪ1. IR (KBr): ν˜ ϭ 1652 br (CO2Ϫ), 1563 w (CϭN), 1482
56.88, H 5.34, N 8.36.
w, 1461 w, 1446 w, 1434 w, 1418 w cmϪ1. UV/Vis (CH2Cl2): λmax.
(log ε) ϭ 233.0 (4.68), 275.0 (4.38), 284.0 (4.38), 546.0 (3.98) nm.
Reaction of 6 with H2O. Formation of [Ru(bdmpza)(OAc)(H2O)-
(PPh3)] (6·H2O): Three equivalents of water (6.00 µL, 0.336 mmol)
were added to an NMR sample of [Ru(bdmpza)(OAc)(PPh3)] (6)
(75 mg, 0.112 mmol) in CD2Cl2 (0.7 mL). NMR spectra were im-
FAB-MS (NBOH): m/z (%) ϭ 760 (100) [Mϩ], 611 (34) [Mϩ
Ϫ
O2CC(O)Ph]. C38H35N4O5PRu (759.76): calcd. C 60.07, H 4.64, N
7.37; found C 60.04, H 4.90, N 7.57.
mediately recorded, showing new signals besides those of 6, due to Complex 8 was also obtained in similar yield and purity either by
the presence of 6·H2O. 1H NMR (CD2Cl2, 400 MHz): δ ϭ 1.50,
reaction of the chloro complex 1 with thallium benzoylformate (4)
1.65, 2.06, 2.25, 2.45 (s, some signals are broad and covered, 5 ϫ or by reaction of benzoylformic acid with 6 or 7. Crystals of 8
CH3 and H2O), 5.80 (s, 1 H, Hpz or HpzЈ), 5.89 (s, 1 H, Hpz or
suitable for X-ray structure determination were obtained from a
HpzЈ), 6.41 (s, 1 H, CH), 7.05Ϫ7.40 (m, 15 H, PPh3) ppm. 13C solution of 1,2-dichloroethane with traces of MeOH and H2O
NMR (CD2Cl2, 100.5 MHz): δ ϭ 10.9, 12.9, 13.0, 14.0 (4 ϫ CH3), (400:2:1, v/v/v).
24.8 (AcϪCH3), 69.5 (CH), 108.8, 109.2 (C4 and C4Ј), PPh3 signals
[Ru(bdmpza){O2CC(O)CH2CH2CO2H}(PPh3)] (9): Reaction of
[Ru(bdmpza)Cl(PPh3)2] (1) (405 mg, 0.446 mmol), thallium acetate
covered, 141.8, 143.7 (C5 and C5Ј), 154.5, 159.1 (C3 and C3Ј), 168.7
(CO2Ϫ), 187.4 (CO2Ϫ) ppm. 31P NMR (CD2Cl2, 161.8 MHz): δ ϭ
(2) (130 mg, 0.493 mmol) and 2-oxoglutaric acid (80.0 mg,
57.1 ppm. Crystallisation of 6 with CH2Cl2/hexane under humid
0.548 mmol) in CH2Cl2 (20 mL) according to method C yielded
conditions yielded yellow crystals of the adduct 6·H2O. M.p.
product 9 as brownish-red microcrystalline powder after 24 h. Yield
200Ϫ205 °C (dec.). FAB-MS (NBOH): m/z (%) ϭ 748 (18) [Mϩ
ϩ
320 mg (95%); m.p. 150Ϫ160 °C (dec.). 1. Isomer: 1H NMR
(CD2Cl2, 400 MHz): δ ϭ 1.67 (s, 3 H, C3ϪCH3), 1.82 (s, 3 H,
H2O ϩ HOAc], 670 (100) [Mϩ], 611 (31) [Mϩ Ϫ OAc], 566 (37)
[Mϩ Ϫ CO2 Ϫ HOAc]. Crystals: C32H33N4O4PRu·CH2Cl2·H2O
(772.63): calcd. C 51.30, H 4.83, N 7.25; found C 51.56, H 4.54,
N 7.30.
3
3
C3ЈϪCH3), 2.05 (ddd, JAB ϭ 21.1, JH,H ϭ 5.3, JH,H ϭ 5.3 Hz, 1
H, CH2ϪCO), 2.26 (ddd, JAB ϭ 17.6, 3JH,H ϭ 5.3, 3JH,H ϭ 5.3 Hz,
1 H, CH2ϪCOOH), 2.34 (s, 3 H, C5ЈϪCH3), 2.37 (ddd, JAB ϭ 17.6,
3
[Ru(bdmpza)(O2CPh)(PPh3)] (7): Reaction of [Ru(bdmpza)-
Cl(PPh3)2] (1) (493 mg, 0.543 mmol) with thallium benzoate (3)
3JH,H ϭ 8.8, JH,H ϭ 5.4 Hz, 1 H, CH2ϪCOOH), 2.40 (s, 3 H,
3
3
C5ϪCH3), 2.95 (ddd, JAB ϭ 21.1, JH,H ϭ 8.8, JH,H ϭ 5.4 Hz, 1
(212 mg, 0.651 mmol) in CH2Cl2 (40 mL) according to method B H, CH2ϪCO), 5.72 (s, 1 H, Hpz), 5.92 (s, 1 H, HpzЈ), 6.51 (s, 1 H,
yielded product 7 as a pale yellow microcrystalline powder after
60 h. Yield 298 mg (75%); m.p. 130 °C (dec.). 1H NMR (CDCl3,
600 MHz): δ ϭ 1.87 (s, 3 H, C3ϪCH3), 2.22 (s, 3 H, C3ЈϪCH3),
CH), 7.08 (m, 6 H, o-Ph), 7.22 (m, 6 H, m-Ph), 7.32 (m, 3 H, p-
Ph) ppm. 13C NMR (CD2Cl2, 100.5 MHz): δ ϭ 11.0 (C5ЈϪCH3),
11.6 (C5ϪCH3), 13.0 (C3ЈϪCH3), 13.9 (C3ϪCH3), 26.9
2.45 (s, 3 H, C5ϪCH3), 2.50 (s, 3 H, C5ЈϪCH3), 5.71 (s, 1 H, Hpz), (CH2ϪCO2H), 34.5 (CH2ϪCO), 68.6 (CH), 109.2 (C4), 109.5 (d,
6.05 (s, 1 H, HpzЈ), 6.38 (s, 1 H, CH), 7.13Ϫ7.51 (m, 20 H, Ph & 4JC,P ϭ 2.7 Hz, C4Ј), 128.6 (d, JC,P ϭ 9.3 Hz, m-PPh3), 130.1 (d,
3
PPh3) ppm. 13C NMR (CDCl3, 150.9 MHz): δ ϭ 11.2 (C5ϪCH3), 4JC,P ϭ 2.5 Hz, p-PPh3,), 131.0 (d, JC,P ϭ 40.7 Hz, i-PPh3), 134.1
1
11.5 (C5ЈϪCH3), 13.0 (C3ЈϪCH3), 14.8 (C3ϪCH3), 68.9 (CH), (d, JC,P ϭ 10.1 Hz, o-PPh3), 142.2 (C5Ј), 144.4 (C5), 155.0 (d,
2
108.1 (C4), 109.2 (C4Ј), 127.1 (m-Ph), 127.5 (o-Ph), 127.7 (d, 3JC,P ϭ 3JC,P ϭ 2.5 Hz, C3Ј), 159.3 (C3), 169.2 (CO2Ϫ), 169.3 (CO2Ϫ), 174.1
9.2 Hz, m-PPh3), 129.0 (p-PPh3), 131.1 (p-Ph), 132.1 (i-Ph), 134.2
(CO2H), 215.5 (CϭO) ppm. 31P NMR (CDCl3, 161.8 MHz): δ ϭ
(br., o-PPh3), 140.8 (C5), 142.2 (C5Ј), 155.3 (C3Ј), 158.3 (C3), 168.2 58.2.
(CO2Ϫ), 183.8 (CO2Ϫ) ppm. 31P NMR (CDCl3, 161.8 MHz): δ ϭ
2. Isomer: 1H NMR (CD2Cl2, 400 MHz): δ ϭ 1.76 (s, 3 H,
60.2 ppm. IR (CH2Cl2): ν˜ ϭ 1662 vs (CO2Ϫ), 1645 w, 1563 w (Cϭ
C3ϪCH3), 1.84 (s, 3 H, C3ЈϪCH3), 2.36 (s, 3 H, C5ЈϪCH3), 2.41
(s, 3 H, C5ϪCH3), 3H covered by the other isomer, 2.83 (ddd,
N), 1505 w, 1501 w, 1482 w, 1463 w, 1435 m, 1428 m, 1419 w cmϪ1
.
IR (KBr): ν˜ ϭ 1671 vs (CO2Ϫ), 1561 w (CϭN), 1499 w, 1482 w,
1460 w, 1431 m, 1421 sh cmϪ1. UV/Vis (CH2Cl2): λmax. (log ε) ϭ
235.0 (4.43), 316.0 (3.91) nm. FAB-MS (NBOH): m/z (%) ϭ 732
3
3
JAB ϭ 21.7, JH,H ϭ 8.5, JH,H ϭ 6.2 Hz, 1 H, CH2ϪCO), 5.74 (s,
1 H, Hpz), 5.91 (s, 1 H, HpzЈ), 6.50 (s, 1 H, CH), 7.08 (m, 6 H, o-
Ph), 7.22 (m, 6 H, m-Ph), 7.32 (m, 3 H, p-Ph) ppm. 13C NMR
(CD2Cl2, 100.5 MHz): δ ϭ 11.0 (C5ЈϪCH3), 11.6 (C5ϪCH3), 12.9
(C3ЈϪCH3), 13.8 (C3ϪCH3), 26.8 (CH2ϪCO2H), 34.6 (CH2ϪCO),
(100) [Mϩ], 611 (41) [Mϩ Ϫ O2CPh], 566 (38) [Mϩ Ϫ CO2
Ϫ
HO2CPh]. C37H35N4O4PRu·H2O (749.77): calcd. C 59.27, H 4.97,
N 7.47; found C 59.30, H 5.30, N 7.46.
4
68.8 (CH), 108.9 (C4), 109.5 (d, JC,P ϭ 2.9 Hz, C4Ј), 128.7 (d,
3
[Ru(bdmpza){O2CC(O)Ph}(PPh3)] (8): Reaction of [Ru(bdmpza)-
Cl(PPh3)2] (1) (333 mg, 0.367 mmol), thallium acetate (2) (115 mg,
3JC,P ϭ 12.2 Hz, m-PPh3), 130.0 (p-PPh3), 132.2 (d, JC,P
ϭ
10.0 Hz, o-PPh3), 141.9 (C5Ј), 143.6 (C5), 155.2 (d, JC,P ϭ 2.6 Hz,
3
0.437 mmol) and benzoylformic acid (69.0 mg, 0.460 mmol) in C3Ј), 157.9 (C3), 167.5 (CO2Ϫ), 168.6 (CO2Ϫ), 173.6 (CO2H), 216.8
CH2Cl2 (30 mL) according to method C yielded product 8 as a
dark purple microcrystalline powder after 2 h. Yield 253 mg (91%);
(CϭO) ppm. 31P NMR (CDCl3, 161.8 MHz): δ ϭ 57.1 ppm. IR
(CH2Cl2): ν˜ ϭ 1657 vs (CO2Ϫ), 1563 w (CϭN), 1483 w, 1463 w,
m.p. 240 °C (dec.). 1H NMR (CDCl3, 600 MHz): δ ϭ 1.88 (s, 3 H, 1435 m, 1417 w cmϪ1. IR (KBr): ν˜ ϭ 1653 vs (CO2Ϫ), 1560 w (Cϭ
C3ЈϪCH3), 1.89 (s, 3 H, C3ϪCH3), 2.47 (s, 3 H, C5ϪCH3), 2.49 (s, N), 1482 w, 1465 w, 1436 w, 1420 w cmϪ1. UV/Vis (CH2Cl2): λmax.
2156
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2004, 2151Ϫ2159