Organometallics
Article
Ar-H), 2.94 (dt, 2H, 2JHH = 16.0 Hz, 2JHP = 4.0 Hz, PCH2), 2.44−2.36
(m, 2H, CH of iPr), 1.92 (d, 2H, 2JHH = 16.0 Hz, PCH2), 1.37 (q, 6H,
3JHH = 8.0 Hz, CH3 of iPr), 1.31−1.24 (m, 2H, CH of iPr), 1.08 (q,
CD2Cl2): δ 7.55 (t, 6H, 3JHH = 8.0 Hz, ortho-H of PPh3), 7.27 (t, 3H,
3JHH = 8.0 Hz, para-H of PPh3), 7.16 (t, 6H, 3JHH = 8.0 Hz, meta-H of
3
PPh3), 6.94 (d, 1H, 3JHH = 8.0 Hz, Ar-H), 6.60 (t, 1H, JHH = 8.0 Hz,
3
6H, 3JHH = 8.0 Hz, CH3 of iPr), 0.91−0.85 (m, 12H, CH3 of iPr). 31
P
Ar-H), 6.20 (d, 1H, JHH = 8.0 Hz, Ar-H), 2.96−2.92 (m, 1H, CH of
2
iPr), 2.43−2.34 (m, 1H, CH of iPr), 1.69−1.58 (m, 2H, CH of iPr),
NMR (162 MHz, CD2Cl2): δ 80.6 (t, JPP = 32.4 Hz, 1P, PPh3), 43.7
(d, 2JPP = 32.4 Hz, 1P, P of ligand). 13C NMR (101 MHz, CD2Cl2): δ
152.7, 137.6, 134.8, 129.4, 128.5, 127.4, 122.0, 121.2, 35.9, 26.2, 25.8,
20.9, 20.1, 19.5, 18.0. Anal. Calcd for C38H50ClP3Ru: C, 61.99; H, 6.85.
Found: C, 62.31; H, 6.95.
3
1.32 (dd, 3H, JHH = 8.0 Hz, CH3 of iPr), 1.22−1.11 (m, 9H, CH3 of
3
iPr), 1.06−1.01 (m, 6H, CH3 of iPr), 0.94 (dd, 3H, JHH = 8.0 Hz,
CH3 of iPr), 0.48 (dd, 3H, 3JH2H = 8.0 Hz, CH3 of iPr). 31P NMR (162
2
MHz, CD2Cl2): δ 168.7 (dd, JPP = 37.3 Hz and JPP = 299.7 Hz, 1P,
P-O), 90.4 (dd, 2JPP = 26.7 Hz and 2JPP = 298.9 Hz, 1P, P-S), 76.4 (dd,
Synthesis of Complex (iPrPCP)RuCl(NBD) (3c).
2
2JPP = 26.7 Hz and JPP = 37.3 Hz, 1P, PPh3). 13C NMR (101 MHz,
CD2Cl2): δ 135.9, 134.3, 134.0, 129.6, 129.1, 128.9, 127.6, 123.3,
117.1, 108.1, 32.3, 31.0, 30.2, 27.6, 20.8, 20.6, 19.2, 19.0, 18.5, 17.4,
16.4. Anal. Calcd for C36H46ClOP3RuS: C, 57.17; H, 6.13. Found: C,
57.00; H, 6.06.
A mixture of (iPrPCP)RuCl(PPh3) (2c; 2.69 g, 3.66 mmol), CuCl
(1.87 g, 18.7 mmol), and NBD (1.87 mL, 18.32 mmol) in 30 mL of
dry CH2Cl2 was stirred at room temperature for 12 h. The insoluble
material was removed by filtration through a pad of Celite, the filtrate
was collected, and the volatiles were removed through evaporation
under vacuum. The residue was purified by column chromatography
on neutral alumina with diethyl ether as eluent to afford the product as
an orange solid (1.35 g, 65%). 1H NMR (400 MHz, C6D6): δ 6.80 (d,
Synthesis of Complex (iPrPSCOP)RuCl(NBD) (3d).
A mixture of (iPrPSCOP)RuCl(PPh3) (2d; 2.68 g, 3.55 mmol), CuCl
(1.81 g, 18.1 mmol), and NBD (1.81 mL, 17.73 mmol) in 30 mL of
dry CH2Cl2 was stirred at 50 °C for 12 h. The insoluble material was
removed by filtration through a pad of Celite, the filtrate was collected,
and the volatiles were removed through evaporation under vacuum.
The residue was purified by column chromatography on neutral
alumina with diethyl ether as eluent to afford the product as an orange
solid (1.21 g, 58%). 1H NMR (400 MHz, CD2Cl2): δ 6.75 (d, 1H, 3JHH
= 8.0 Hz, Ar-H), 6.47 (m, 2H, Ar-H), 4.48 (s, 1H, vinylic NBD), 4.17
(s, 1H, vinylic NBD), 3.75 (s, 1H, P-CH), 3.72−3.66 (m, 1H, P-CH),
3.59 (s, 1H, P-CH), 3.54−3.41 (m, 2H, P-CH and CH of NBD),
3.38−3.29 (m, 1H, CH of NBD), 2.92 (s, 1H, vinylic NBD), 2.33 (s,
3
3
2H, JHH = 8.0 Hz, Ar-H), 6.56 (t, 1H, JHH = 8.0 Hz, Ar-H), 4.13 (s,
2
2
2H, vinylic NBD), 3.76 (dt, 2H, JHH = 16.0 Hz, JHP = 4.0 Hz, P-
CH2), 3.64 (s, 2H, P-CH), 3.32 (dt, 2H, 2JHH = 16.0 Hz, 2JHP = 4.0 Hz,
P-CH2), 3.15−2.98 (m, 6H, P-CH, vinylic NBD, CH of NBD), 1.72
(q, 6H, 3JHH = 8.0 Hz, CH3 of iPr), 1.48 (q, 6H, 3JHH = 8.0 Hz, CH3 of
iPr), 1,27 (q, 6H, 3JHH = 8.0 Hz, CH3 of iPr), 1.18−1.11 (q, 6H, 3JHH
=
8.0 Hz, CH3 of iPr), 1.06 (m, 2H, CH2 of NBD). 31P NMR (162 MHz,
CD2Cl2): δ 64.5 (s). 13C NMR (101 MHz, CD2Cl2): δ 173.4, 147.5,
122.3, 120.5, 59.0, 58.0, 49.4, 46.1, 37.7, 28.8, 25.5, 21.6, 20.8, 20.5,
20.0. Anal. Calcd for C27H43ClP2Ru: C, 57.28; H, 7.66. Found: C,
57.26; H, 7.65.
3
1H, vinylic NBD), 1.76 (dd, 3H, JHH = 8.0 Hz, CH3 of iPr), 1.71−
3
Synthesis of Complex (iPrPCP)RuH(NBD) (4c).
1.64 (m, 6H, CH3 of iPr), 1.60 (dd, 3H, JHH = 8.0 Hz, CH3 of iPr),
3
1.43−1.35 (m, 9H, CH3 of iPr), 0.99 (dd, 3H, JHH = 8.0 Hz, CH3 of
iPr), 1.00 (t, 2H, 3JHH = 8.0 Hz, CH2 of NBD). 31P NMR (162 MHz,
CD2Cl2): δ 187.1 (d, 2JPP = 217.9 Hz, 1P, P-O), 116.9 (d, 2JPP = 217.9
Hz, 1P, P-S). 13C NMR (101 MHz, CD2Cl2): δ 134.3, 129.6, 127.6,
123.4, 116.5, 107.8, 63.7, 63.0, 57.2, 47.7, 47.3, 46.7, 45.7, 34.4, 34.1,
31.8, 28.8, 21.2, 21.0, 19.8, 19.4, 19.0, 18.6, 18.2, 15.5. Anal. Calcd for
C25H39ClOP2RuS: C, 51.23; H, 6.71. Found: C, 51.40; H, 6.66.
Synthesis of Complex (iPrPSCOP)RuH(NBD) (4d).
A mixture of (iPrPCP)RuCl(NBD) (3c; 1.35 g, 2.38 mmol) and
NaBH4 (0.90 g, 23.8 mmol) in 30 mL of dry THF was stirred at room
temperature for 12 h. After evaporation of the solvent under vacuum,
the residue was dissolved in toluene and filtered through a pad of
Celite. The filtrate was collected, and the volatiles were removed
through evaporation under vacuum. The solid was washed with diethyl
ether (9 mL) and dried in vacuo for 30 min to give an off-white solid
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as the product (1.09 g, 86%). H NMR (400 MHz, CD2Cl2): δ 6.72
A mixture of (iPrPSCOP)RuCl(PPh3) (3d; 1.21 g, 2.06 mmol) and
NaBH4 (0.78 g, 20.63 mmol) in 30 mL of dry THF was stirred at 80
°C for 4 h. After evaporation of the solvent under vacuum, the residue
was dissolved in toluene and filtered through a pad of Celite. The
filtrate was collected, and the volatiles were removed through
evaporation under vacuum. The solid was washed with diethyl ether
(9 mL) and dried in vacuo for 30 min to give an off-white solid as the
product (1.08 g, 92%). 1H NMR (400 MHz, CD2Cl2): δ 6.71 (d, 1H,
3JHH = 8.0 Hz, Ar-H), 6.46 (t, 1H, 3JHH = 8.0 Hz, Ar-H), 6.34 (d, 1H,
3JHH = 8.0 Hz, Ar-H), 3.79 (s, 2H, vinylic NBD), 3.72 (s, 1H, P-CH),
3.71−3.64 (m, 1H, P-CH), 3.58 (s, 1H, P-CH), 3.49−3.39 (m, 3H, P-
CH and CH of NBD), 2.71−2.64 (m, 1H, vinylic NBD), 2.50−2.44
(m, 1H, vinylic NBD), 1.69−1.61 (m, 12H, CH3 of iPr), 1.14 (d, 3H,
3JHH = 8.0 Hz, CH3 of iPr), 1.07 (dd, 3H, 3JHH = 8.0 Hz, CH3 of iPr),
0.99 (dd, 3H, 3JHH = 8.0 Hz, CH3 of iPr), 0.94 (d, 3H, 3JHH = 8.0 Hz,
3
(d, 2H, 3JHH = 8.0 Hz, Ar-H), 6.44 (t, 1H, JHH = 8.0 Hz, Ar-H), 3.68
(s, 2H, vinylic NBD), 3.55 (s, 2H, P-CH), 3.41−3.34 (m, 4H, P-CH2
and P-CH), 3.21−3.13 (m, 2H, P-CH2), 2.93 (s, 2H, vinylic NBD),
2.25−2.07 (m, 2H, CH of NBD), 1.62−1.54 (m, 12H, CH3 of iPr),
3
1.10 (q, 6H, JHH = 8.0 Hz, CH3 of iPr), 1.03 (s, 2H, CH2 of NBD),
0.72 (q, 6H, 3JHH = 8.0 Hz, CH3 of iPr), −11.95 (t, 2JHP = 28.0 Hz, 1H,
Ru-H); 31P NMR (162 MHz, CD2Cl2): δ 84.0 (s). 13C NMR (101
MHz, CD2Cl2): δ 181.4, 146.5, 120.3, 119.8, 60.1, 49.3, 47.7, 47.1,
42.8, 31.8, 26.5, 21.2, 20.4, 19.0, 1.2. Anal. Calcd for C27H44P2Ru: C,
61.00; H, 8.34. Found: C, 61.13; H, 8.38.
Synthesis of Complex (iPrPSCOP)RuCl(PPh3) (2d).
CH3 of iPr), 0.90 (d, 3JHH = 8.0 Hz, CH2 of NBD), −12.76 (t, 1H, 2JHP
A mixture of iPrPSCOP-H (1d; 1.50 g, 4.18 mmol) and RuCl2(PPh3)3
(3.63 g, 3.79 mmol) in 30 mL of dry THF was stirred at 80 °C for 8 h.
After evaporation of the solvent under vacuum, the residue was
purified by column chromatography on neutral alumina, with n-hexane
as eluent to remove PPh3, and then with THF as eluent to afford the
product as a dark green solid (2.68 g, 85% yield). 1H NMR (400 MHz,
2
= 32.0 Hz, Ru-H). 31P NMR (162 MHz, CD2Cl2): δ 205.8 (d, JPP
=
183.1 Hz, 1P, P-O), 135.7 (d, JPP = 183.1 Hz, 1P, P-S). 13C NMR
(101 MHz, CD2Cl2): δ 133.5, 131.7, 129.2, 122.2, 115.1, 105.8, 60.5,
58.5, 56.6, 49.2, 48.8, 48.2, 48.1, 36.6, 33.7, 32.0, 31.3, 21.7, 21.5, 20.1,
19.5, 19.1, 18.6, 17.7, 15.5. Anal. Calcd for C25H40OP2RuS: C, 54.43;
H, 7.31. Found: C, 54.73; H, 6.94.
2
F
Organometallics XXXX, XXX, XXX−XXX