Organometallics
Article
1
22.5 Hz, 1H, RuH), 2.73−2.64 (m, 4H, CH2), 3.52 (t, 3JH−H = 4.9 Hz,
2H, CH2), 3.95 (t, 3JH−H = 4.9 Hz, 2H, CH2), 6.45 (d, 3JH−H = 7.8 Hz,
2H, o-OPh), 6.52 (d, 3JH−H = 7.8 Hz, 2H, o-OPh), 6.59 (d, 3JH−H = 2.1
PPh3), 138.29 (t, JC−P = 17.1 Hz, ipso-C, PPh3), 197.15 (m, NCN
carbon). 31P{1H} NMR (162 M, CD2Cl2): 43.98 (br, PPh3, major
isomer), 43.75 (PPh3, minor isomer). Anal. Calcd for
C45H45Cl3N2O2P2Ru (915.23): C, 59.05; H, 4.96; N, 3.06. Found:
C, 58.67; H, 5.12; N, 3.07.
Hz, 1H, NCH), 6.90 (t, 3JH−H = 7.4 Hz, 2H, p-OPh), 6.99 (d, 3JH−H
=
2.1 Hz, 1H, NCH), 7.32−7.23 (m, 18H, o-PPh3, p-PPh3), 7.23−7.16
(apparent quartet, 4H, m-OPh), 7.49−7.42 (m, 12H, m-PPh3).
13C{1H} NMR (CD2Cl2): 47.12 (CH2), 49.31 (CH2), 65.23 (CH2),
67.40 (CH2), 114.56 (OPh), 114.84 (OPh), 120.50 (NCH), 120.56
(NCH), 121.11 (OPh), 121.37 (OPh), 128.20 (vt, JC−P = 5.9 Hz, m-
PPh3), 129.33 (p-PPh3), 129.59 (OPh), 129.72 (OPh), 134.76 (t, JC−P
= 5.9 Hz, o-PPh3), 137.72 (t, 1JC−P = 18.3 Hz, ipso-PPh3), 158.25 (ipso-
OPh), 158.42 (ipso-OPh). 31P{1H} NMR (CD2Cl2): 47.06. Anal.
Calcd for C55H51ClN2O2P2Ru (970.47): C, 68.06; H, 5.31; N, 2.89.
Found: C, 66.52; H, 5.19; N, 3.25.
4h. Compound 3h (0.190 g, 0.477 mmol) and RuHCl(PPh3)3
(0.390 g, 0.423 mmol) yielded a yellow solid (0.064 g, 17%). 1H NMR
2
(CD2Cl2): −22.98 (t, JP−H = 24.0 Hz, Ru−H), 1.63 (s, 3H, CCH3),
1.85 (s, 3H, CCH3), 2.61 (t, JH−H = 6.4 Hz, 2H, CH2), 2.76 (s, 3H,
3
OCH3), 2.82 (s, 3H, OCH3), 2.83 (t, 3JH−H = 6.4 Hz), 3.31−3.34 (m,
2H, CH2), 3.41−3.45 (m, 2H, CH2), 7.18−7.22 (m, 12H, o-PPh3),
7.26−7.30 (m, 6H, p-PPh3), 7.43−7.50 (m, 12H, m-PPh3). 13C{1H}
NMR (CD2Cl2): 9.23 (CCH3), 9.99 (CCH3), 46.08 (CH2), 46.24
(CH2), 58.18 (OCH3), 60.02 (OCH3), 69.75 (CH2), 73.52 (CH2),
124.56 (CCH3), 123.56 (CCH3), 127.50 (t, J = 4.3 Hz, PPh3), 128.58
(PPh3), 134.86 (t, J = 5.6 Hz, PPh3), 139.11 (t, J = 16.8 Hz, PPh3),
190.61 (m, NCN carbon, observed in HMBC NMR spectroscopy).
31P{1H} NMR (CD2Cl2): 45.46. Anal. Calcd for C47H51ClN2O2P2Ru
(874.39): C, 64.56; H, 5.88; N, 3.20. Found: C, 63.67; H, 6.22; N,
3.15.
4e. Compound 3e (0.284 g, 0.459 mmol) and RuHCl(PPh3)3
1
(0.326 g, 0.353 mmol) yielded a red solid (55 mg, 14%). H NMR
(CD2Cl2): −31.98 (t, 2JP−H = 23.7 Hz, 1H, RuH), 1.12 (d, 3JH−H = 6.8
Hz, 12H, CH(CH3)2), 1.16 (d, 3JH−H = 6.8 Hz, 12H, CH(CH3)2), 2.51
(t, 3JH−H = 6.2 Hz, 2H, CH2), 2.70 (t, 3JH−H = 6.2 Hz, 2H, CH2), 2.87
(septet, 3JH−H = 6.8 Hz, 2H, CH(CH3)2), 2.97 (septet, 3JH−H = 6.8 Hz,
3
3
Synthesis of RuHCl(CO)(PPh3)2(Im(OMe)2) (5). Compound 4a
(0.179 g, 0.546 mmol) in methylene chloride (5 mL) was added to a
slurry of RuHCl(CO)(PPh3)3 (0.436 g, 0.458 mmol) in methylene
chloride (5 mL). The mixture was stirred for 16 h to produce a yellow
suspension. The solid was filtered off, and the solution was
concentrated to yield an off-white solid. The solid was washed with
pentane (2 × 10 mL), dried, and taken up in THF (5 mL), and this
solution was filtered through two plugs of neutral alumina. The
solution was concentrated to give a pure white solid (0.352 g, 88%).
Crystals were grown from CH2Cl2/Et2O. 1H NMR (CD2Cl2): −15.13
2H, CH(CH3)2), 3.23 (t, JH−H = 4.4 Hz, 2H, CH2), 3.94 (t, JH−H
=
4.4 Hz, 2H, CH2), 6.80 (d, 3JH−H = 1.7 Hz, 1H, NCH), 7.00−7.07 (m,
5H, 4 OArH, 1 NCH), 7.22−7.34 (m, 20H, 18 o-PPh3, p-PPh3, 2
OArH), 7.44−7.48 (m, 12H, m-PPh3). 13C{1H} NMR: the compound
is not stable enough in solution to obtain 13C data. 31P{1H} NMR:
47.36 (br s). Anal. Calcd for C67H78ClN2O2P2Ru (1138.80): C, 70.66;
H, 6.64; N, 2.46. Found: C, 70.11; H, 6.90; N, 2.62.
Synthesis of RuHCl(PPh3)2(Y2Im(OMe)2) (Y2Im(OMe)2
=
Y2C3(NCH2CH2OMe)2; Y2 = C6H4 (4f), Y = Cl (4g), Me (4h)).
These compounds were prepared in a similar fashion with minor
changes to conditions. Thus, only one is detailed. Compound 6f
(0.296 g, 0.783 mmol) and RuHCl(PPh3)3 (0.700 g, 0.759 mmol)
were combined, and toluene (20 mL) was added. The suspension was
stirred for 3 days at room temperature, and a green precipitate was
collected by filtration (0.358 g). The crude product was dissolved in
3.0 mL of dichloromethane, which was layered with 17 mL of diethyl
ether. The mixture was left at room temperature for 1 day, resulting in
the formation of yellow crystals (0.193 g, 28%).
2
3
(t, JP−H = 19.5 Hz, 1H, RuH), 2.76 (pst, JH−H = 5.0 Hz, 2H, CH2),
2.82 (s, 3H, CH3), 2.91 (pst, JH−H = 3.8 Hz, 2H, CH2), 3.10 (s, 3H,
3
3
3
OCH3), 3.50 (ps t, JH−H = 4.4 Hz, 2H, CH2), 3.57 (ps t, JH−H = 4.5
Hz, 2H, CH2), 6.57 (s, 1H, NCH), 6.66 (s, 1H, NCH), 7.26−7.30 (m,
12H, o-PPh3), 7.34−7.37 (m, 6H, p-PPh3), 7.45−7.50 (m, 12H, m-
PPh3). 13C{1H} NMR: 49.05 (CH2), 51.37 (CH2), 58.08 (CH3), 58.20
(CH3), 71.21 (CH2), 73.20 (CH2), 122.35 (CH, Im), 123.28 (CH,
Im), 127.80 (t, JC−P = 4.4 Hz, o-PPh3), 129.35 (s, p-PPh3), 134.24 (t, J
= 5.9 Hz, m-PPh3), 136.67 (t, J = 20.15 Hz, ipso-PPh3), 183.78 (t, J
=13.6 Hz, NCN), 204.76 (t, J = 16.7 Hz, Ru(CO)). 31P NMR: 42.57
(br s). IR (cm−1): 1925. Anal. Calcd for C46H47ClN2O3P2Ru·CH2Cl2
(958.28): C, 58.85; H, 5.15; N, 2.92. Found: C, 58.43; H, 5.22; N,
2.59.
Synthesis of RuHCl(CO)(SIMes)(Im(OMe)2) (6). Compound 5
(0.226 g, 0.258 mmol) and SIMes (0.165 g, 0.538 mmol) were
combined in THF (25 mL), and the mixture was heated at 60 °C for
16 h to produce a bright yellow suspension. All volatiles were removed
under vacuum, the residue was extracted with Et2O (5 mL), and the
extract was filtered through a plug of Celite. The yellow solution was
concentrated to dryness and taken up in methylene chloride (1 mL).
Layering pentane on top and letting the solution sit at −40 °C
produced orange crystals (0.116 g, 69%). 1H NMR (CD2Cl2): −25.46
(s, 1H, RuH), 2.30 (s, 6H, CH3, Mes), 2.40 (s, 6H, CH3, Mes), 2.53
(s, 6H, CH3, Mes), 3.13 (s, 6H, OCH3), 3.16 (br s, 4H, CH2), 3.68
(br. s, 4H, CH2), 4.01 (s, 4H, NCH2CH2N), 6.76 (s, 2H, CH, Im),
6.91 (s, 2H, CH, Mes), 6.97 (s, 2H, CH, Mes). 13C{1H} NMR: 18.65
(CH3, Mes), 20.83 (CH3, Mes), 50.12 (CH2), 50.92 (NCH2CH2N),
58.42 (OCH3), 71.79 (CH2), 120.82 (CH, Mes), 128.95 (CH, Im),
128.99 (CH, Im), 136.82 (ipso-C, Mes), 137.37 (ipso-C, Mes), 137.47
(ipso-C, Mes), 137.54 (ipso-C, Mes), 190.10 (NCN), 201.98 (CO),
219.80 (NCN). IR (cm−1): 1884. Anal. Calcd for C31H43ClN4O3R
(656.22): C, 56.74; H, 6.60; N, 8.54. Found: C, 57.07; H, 6.86; N,
8.62.
1
2
4f. H NMR (CD2Cl2): −22.59 (t, JP−H = 23.8 Hz, 1H, Ru−H),
3
2.61 (t, JH−H = 6.6 Hz, 2H, CH2), 2.81 (s, 3H, OCH3), 2.87 (s, 3H,
3
3
OCH3), 3.10 (t, JH−H = 6.6 Hz, 2H, CH2), 3.58 (t, JH−H = 4.1 Hz,
2H, CH2), 3.69 (t, 3JH−H = 4.1 Hz, 2H, CH2), 6.63 (d, 3JH−H = 7.8 Hz,
3
3
1H, CH), 6.85 (d, JH−H = 7.8 Hz, 1H, CH), 6.95 (t, JH−H = 7.8 Hz,
1H, CH), 7.03 (t, 3JH−H = 7.8 Hz, CH), 7.08−7.12 (m, 12H, o-PPh3),
7.22−7.25 (m, 6H, p-PPh3), 7.39−7.47 (m, 12H, m-PPh3). 13C{1H}
NMR (CD2Cl2): 45.76 (CH2), 45.83 (CH2), 58.31 (OCH3), 59.97
(OCH3), 68.93 (CH2), 73.09 (CH2), 105.64 (CH), 108.88 (CH),
120.57 (NC), 120.67 (NC), 127.67 (vt, JC−P = 4.1 Hz, m-PPh3),
128.85 (p-PPh3), 134.67 (vt, JC−P = 5.6 Hz, o-PPh3), 136.13 (CH),
136.21 (CH), 137.88 (vt, JC−P = 17.3 Hz, ipso-PPh3), 209.82 (td, JC−P
2
= 11.9 Hz, JC−H(hydride) = 4.4 Hz, NCN). 31P{1H} NMR (CD2Cl2):
44.65. Anal. Calcd for C49H49ClN2O2P2Ru (896.40): C, 65.65; H,
5.51; N, 3.13. Found: C, 64.91; H, 5.56; N, 3.06.
4g. Compound 3g (0.190 g, 0.431 mmol) and RuHCl(PPh3)3
(0.394 g, 0.427 mmol) yielded yellow crystals (0.204 g, 52%). Major:
minor product ratio = 5.7. 1H NMR (CD2Cl2): −22.68 (t, 2JP−H = 23.2
Hz, 0.85 H, Ru−H, major isomer), −22.46 (t, 2JP−H = 23.6 Hz, 0.15 H,
3
Ru−H, minor isomer), 2.63 (t, JH−H = 6.8 Hz, 1.7 H, CH2, major
3
isomer), 2.71 (t, JH−H = 6.7 Hz, 0.3 H, CH2, major isomer), 2.78 (s,
0.4 H, OCH3, minor isomer), 2.80 (s, 2.6 H, OCH3, major isomer),
2.84 (s, 2.6 H, OCH3, major isomer), 2.87 (s, 0.4 H, OCH3, minor
3
isomer), 2.97 (t, JH−H = 6.8 Hz, 2H, CH2), 3.49−3.53 (m, 4 H, 2 ×
CH2), 7.22−7.26 (m, 12H, o-PPh3), 7.30−7.34 (m, 6 H, p-PPh3),
7.47−7.53 (m, 12 H, m-PPh3). 13C{1H} NMR (100 M, CD2Cl2, 53.8
ppm): 46.91 (CH2), 47.11 (CH2), 58.26 (OCH3, minor isomer),
58.31 (OCH3, major isomer), 60.10 (OCH3, major isomer), 60.87
(OCH3, minor isomer), 68.58 (CH2, minor isomer), 68.50 (CH2,
major isomer), 72.66 (CH2, minor isomer), 72.75 (CH2, major
Synthesis of [RuH(Im(OMe)2)(SIMes)][(η6-Ph)BPh3] (8). Com-
pound 7 (0.139 g, 0.156 mmol) in methylene chloride (5 mL) was
added to a slurry of NaBPh4 (0.065 g, 0.190 mmol) in methylene
chloride (5 mL). The mixture was stirred for 16 h at room
temperature, during which time the solution changed from red to
yellow. The mixture was filtered through Celite and concentrated to 2
mL. Pentane (15 mL) was added to precipitate a light yellow solid.
3
isomer), 113.22 (CCl, Im), 114.11 (CCl, Im), 127.75 (t, JC−P = 4.2
Hz, m-C, PPh3), 129.03 (s, p-C, PPh3), 134.72 (t, 2JC−P = 5.4 Hz, o-C,
H
dx.doi.org/10.1021/om400044w | Organometallics XXXX, XXX, XXX−XXX