Article
Organometallics, Vol. 28, No. 17, 2009 5171
materials were dried in vacuo. [(η6-C6Me6)RuCl2]2,28 [(η6-pCy)-
RuCl2(PH2Mes*)],6 [(η6-pCy)OsCl2(PH2Mes*)],6 [(η5-Cp)CoI2-
(PH2Mes*)],7 [(η5-Cp*)RhCl2(PH2Mes*)],7 [(η5-Cp*)IrCl2-
mixture was stirred for 1 h at -78 ꢀC and warmed to room
temperature, solvents were removed in vacuo. The precipitates
were extracted into n-hexane (10 mL), and the dark green
suspension was filtered. After concentration, green crystals
of 4 were obtained at -20 ꢀC (83 mg, 0.12 mmol, 60%). Mp:
g208 ꢀC dec. 1H NMR (250.13 MHz, C6D6, 300 K): δ 0.94 (d,
3JHH = 6.9 Hz, 6 H, pCy-CH(CH3)2), 1.30 (d, 3JHH = 7.1 Hz, 6
H, CH(CH3)2), 1.37 (d, 3JHH = 7.1 Hz, 6 H, CH(CH3)2), 1.57 (s,
9 H, p-C(CH3)3), 1.64 (s, 3 H, pCy-CH3), 1.82 (s, 18 H,
(PH2Mes*)],8
1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene
(IiPr2Me2),29 1,3-dimesityl-imidazol-2-ylidene (IMes),30 and
31
Mes*PH2 were prepared according to literature procedures.
MesPH2 was prepared, analogously to IsPH2,32 by LiAlH4
reduction of MesPCl2. [(η6-pCy)RuCl2]2 was purchased from
Strem and used as received.
[(η6-pCy)RuCl2(PH2Mes)]. MesPH2 (0.219 g, 1.437 mmol)
was added to a dark red suspension of [(η6-pCy)RuCl2]2
(0.400 g, 0.653 mmol) in CH2Cl2 (25 mL), which was stirred
for 1 h at room temperature and filtered to remove insoluble
material. After the solution was concentrated to a few milliliters,
pentanes (30 mL) was added slowly, which resulted in precipita-
tion of an orange powder that was isolated by filtration, washed
with pentanes (25 mL), and dried in vacuo to yield [(η6-pCy)-
RuCl2(PH2Mes)] (0.561 g, 1.22 mmol, 94%). Mp: g163 ꢀC dec.
1H NMR (250.13 MHz, CDCl3, 300 K): δ 1.19 (d, 3JHH = 7.0
Hz, 6 H, CH(CH3)2), 1.99 (s, 3 H, pCy-CH3), 2.34 (s, 3 H,
o-C(CH3)3), 1.89 (s, 6 H, CH3), 2.37 (sp, JHH = 6.9 Hz, 1 H,
pCy-CH(CH3)2), 4.63 (d, 3JHH = 5.7 Hz, 2 H, C6H4), 4.85 (d,
3
3
3JHH = 5.7 Hz, 2 H, C6H4), 5.91 (sp, JHH = 7.1 Hz, 2 H,
NCH(CH3)2), 7.55 (s, 2 H, m-Mes*). 13C{1H} NMR (100.64
MHz, C6D6, 300 K): δ 10.5 (s, dCCH3), 18.9 (s, pCy-CH3), 22.0
(s, NCH(CH3)2), 22.2 (s, NCH(CH3)2), 23.9 (s, pCy-CH(CH3)2),
32.2 (s, p-C(CH3)3), 32.2 (s, CH(CH3)2), 32.7 (d, 4JCP = 7.5 Hz,
o-C(CH3)3), 34.9 (s, p-C(CH3)3), 38.8 (s, o-C(CH3)3), 54.9 (s,
NCH(CH3)2), 76.2, 81.5, 91.7, and 105.9 (s, C6H4), 119.9 (s, m-
Mes*), 124.6 (s, dCCH3), 144.9 (s, p-Mes*), 146.3 (s, o-Mes*),
1
174.1 (d, JCP = 111.3 Hz, i-Mes*), 188.7 (s, N2C). 31P{1H}
3
p-CH3), 2.50 (s, 6 H, o-CH3), 2.70 (sp, JHH = 7.0 Hz, 1 H,
CH(CH3)2), 5.13 (d, 3JHH = 5.7 Hz, 2 H, C6H4), 5.34 (d, 3JHH
NMR (101.3 MHz, C6D6, 300 K): δ 733.5 (s, RudP). HRMS
(EI, 70 eV, m/z): calcd for C39H63N2PRu, 692.3766; found,
692.3707. MS (m/z (%)): 692 (8) [M+], 416 (20) [M+ - PMes*],
283 (8).
=
5.7 Hz, 2 H, C6H4), 5.52 (d, 1JHP = 389.8 Hz, 2 H, PH2), 7.01 (d,
4JHP = 2.3 Hz, 2 H, m-Mes). 13C{1H} NMR (62.90 MHz,
5
CDCl3, 300 K): δ 18.4 (s, pCy-CH3), 21.6 (d, JCP = 1.1 Hz,
[(η6-pCy)(IMes)RudPMes] (5a). A solution of IMes (0.481 g,
1.415 mmol) in toluene (10 mL) was added to a toluene (5 mL)
suspension of the complex [(η6-pCy)RuCl2(PH2Mes)] (0.2125 g,
0.464 mmol) at -78 ꢀC. The mixture was stirred for 0.5 h and
was slowly warmed to room temperature. After 2 days, the
solvent was evaporated in vacuo; the dark brown solid was
extracted with pentanes (20 mL) and filtered (P4 glass filter,
Teflon microfiber, Celite), and after concentration a mixture of
5a and the η6-toluene adduct [(η6-Tol)(IMes)RudPMes]14 (5:1
ratio) was obtained as a dark brown solid (0.180 g, 0.261 mmol,
56%). Data for 5a are as follows. 1H NMR (400.13 MHz, C6D6,
300 K): δ 0.84 (d, 3JHH = 6.9 Hz, 6 H, pCy-CH(CH3)2), 1.51 (s, 3
3
p-CH3), 22.5 (s, CH(CH3)2), 22.9 (d, JCP = 8.2 Hz, o-CH3),
31.0 (s, CH(CH3)3), 85.5 (d, 2JCP = 5.7 Hz, C6H4), 89.1 (d, 2JCP
= 5.3 Hz, C6H4), 97.6 (s, C6H4), 107.7 (d, 2JCP = 1.0 Hz, C6H4),
122.3 (d, 1JCP = 42.3 Hz, i-Mes), 130.1 (d, 3JCP = 7.8 Hz, m-
Mes), 141.4 (d, 2JCP = 7.7 Hz, o-Mes), 141.5 (d, 4JCP = 2.9 Hz,
p-Mes). 31P NMR (101.3 MHz, CDCl3, 300 K): δ -48.0 (t, 1JPH
= 389.9 Hz, PH2). IR (KBr, cm-1): ν 3043.0 (w), 2967.2 (m),
2913.3 (w), 2864.7 (w), 2387.6 (m, P-H), 2353.7 (m, P-H),
1601.4 (m), 1437.9 (s), 1382.3 (s). HR FAB-MS (m/z): calcd for
C19H27PCl2Ru, 458.0271; found, 458.0270. MS (m/z (%)): 458
(70) [M+], 423 (100) [M+ - Cl], 388 (100) [M+ - 2Cl], 271 (35)
[M+- Cl - H2PMes], 154 (90) [H2PMes].
3
H, pCy-CH3), 1.64 (sp, JHH = 6.9 Hz, 1 H, pCy-CH(CH3)2),
[(η6-C6Me6)RuCl2(PH2Mes)]. Analogous to the method de-
scribed for [(η6-pCy)RuCl2(PH2Mes)], [(η6-C6Me6)RuCl2]2
(1.01 g, 1.50 mmol) and MesPH2 (0.464 g, 3.05 mmol) were
used to give [(η6-C6Me6)RuCl2(PH2Mes)] as a yellow powder
(1.29 g, 2.65 mmol, 88%). Mp: g257 ꢀC dec. 1H NMR (250.13
MHz, CDCl3, 300 K): δ 1.92 (s, 18 H, C6(CH3)6), 2.29 (s, 3 H, p-
CH3), 2.39 (s, 6 H, o-CH3), 5.45 (d, 1JHP = 379.7 Hz, 2 H, PH2),
2.12 (s, 6 H, o-CH3MesP), 2.25 (s, 6 H, p-CH3MesN), 2.32 (s, 12
H, o-CH3MesN), 2.37 (s, 3 H, p-CH3MesP), 4.38 (d, 3JHH = 5.9
Hz, 2 H, C6H4), 4.65 (d, 3JHH = 5.9 Hz, 2 H, C6H4), 6.35 (s, 2 H,
NCHd), 6.73 (s, 4 H, m-MesN), 6.94 (s, 2 H, m-MesP). 13C{1H}
NMR (100.64 MHz, C6D6, 300 K): δ 19.5 (s, pCy-CH3), 19.7 (s,
o-CH3NMes), 20.9 (s, o-CH3PMes), 21.3 (s, p-CH3PMes), 21.5
(s, p-CH3NMes), 25.2 (s, pCy-CH(CH3)2), 32.2 (s, pCy-CH-
(CH3)2), 81.1, 83.1, 87.9, and 100.7 (s, C6H4), 122.3 (s, dCH),
127.5 (s, m-MesP), 128.9 (s, m-MesN), 132.3 (s, o-MesP), 132.9
(s, p-MesP), 136.3 (s, i-MesN), 138.0 (s, o-MesN), 138.9 (s,
4
6.95 (d, JHP = 2.1 Hz, 2 H, m-Mes). 13C{1H} NMR (62.90
MHz, CDCl3, 300 K): δ 15.7 (s, C6(CH3)6), 21.6 (s, p-CH3), 23.4
(d, 3JCP = 8.0 Hz, o-CH3), 96.1 (d, 3JCP = 3.5 Hz, C6(CH3)6),
119.3 (d, 1JCP = 38.3 Hz, i-Mes), 129.9 (d, 3JCP = 7.6 Hz, m-
Mes), 141.1 (d, 4JCP = 2.5 Hz, p-Mes), 142.7 (d, 2JCP = 7.4 Hz,
o-Mes). 31P NMR (101.3 MHz, CDCl3, 300 K): δ -53.7 (t, 1JPH
= 379.8 Hz, PH2). IR (KBr, cm-1): ν 3019.1 (w), 2953.2 (m),
2914.4 (m), 2397.3 (m, P-H), 2364.6 (m, P-H), 1601.3 (m),
1447.67 (s), 1383.7 (m). HR FAB-MS (m/z): calcd for
C21H31PCl2Ru, 486.0584; found, 486.0588. MS (m/z (%)): 486
(65) [M+], 451 (50) [M+ - Cl], 413 (50) [M+ - 2HCl], 299 (60)
[M+- 2HCl - H2PMes], 154 (100) [H2PMes].
1
p-MesN), 168.3 (d, JCP = 100.0 Hz, i-MesP), 191.7 (s, N2C).
31P{1H} NMR (101.3 MHz, C6D6, 300 K): δ 724.9 (s, RudP).
HRMS (EI, 70 eV, m/z): calcd for [C40H49N2PRu] - [C9H11P],
540.2072; found, 540.2091. MS (m/z (%)): 540 (16) [M+- PMes],
302 (10) [M+- PMes - 2Mes].
[(η6-C6Me6)(IMes)RudPMes] (5b). A solution of IMes (0.258
g, 0.85 mmol) in toluene (1 mL) was added under argon to a
toluene (2 mL) suspension of the complex [(η6-C6Me6)RuCl2-
(PH2Mes)] (0.136 g, 0.28 mmol) at -78 ꢀC. The mixture was
slowly warmed to room temperature, the resulting dark brown
reaction mixture was filtered (P4 glass filter), and the filtrate was
evaporated in vacuo. Extraction with pentanes (5 mL), filtra-
tion, and concentration at room temperature yielded 5b as a
dark brown solid (0.116 g, 0.162 mmol, 58%). Mp: g198 ꢀC dec.
1H NMR (400.13 MHz, C6D6, 300 K): δ 1.66 (s, 18 H, C6-
(CH3)6), 2.14 (s, 6 H, o-CH3PMes), 2.18 (s, 6 H, p-CH3NMes),
2.21 (s, 6 H, o-CH3NMes), 2.36 (s, 3 H, p-CH3PMes), 2.52 (s, 6
H, o-CH3NMes), 6.33 (s, 2 H, dCH), 6.75 (s, 2 H, m-MesN),
6.79 (s, 2 H, m-MesN), 6.90 (s, 2 H, m-MesP). 13C{1H} NMR
(100.64 MHz, C6D6, 300 K): δ 16.5 (s, C6(CH3)6), 19.9 (s,
o-CH3NMes), 21.0 (s, p-CH3NMes), 21.1 (s, o-CH3NMes),
21.4 (s, p-CH3PMes), 21.5 and 21.6 (s, o-CH3PMes), 90.9
(s, C6Me6), 122.8 (s, dCH), 127.6 (s, m-MesP), 128.4 and
[(η6-pCy)(IiPr2Me2)RudPMes*] (4). A cold solution of
IiPr2Me2 (0.119 g, 0.66 mmol) in toluene (4 mL) was added to
an orange toluene (5 mL) suspension of the complex [(η6-
pCy)RuCl2(PH2Mes*)] (0.117 g, 0.20 mmol) at -78 ꢀC, which
immediately resulted in a color change to green. After the
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