(dd, 1H, J 8, 1.5, Ar-3-H ). MS (FABϩ): m/z 419 [M]ϩ and 384
[M Ϫ Cl]ϩ.
Ar-3-H ϩ py-3,5-H ), 7.91 (m, 1H, py-4-H ) 8.91 [8.60] (br, 2H,
py-1,6-H ). MS (FABϩ): m/z 426, [M Ϫ py]ϩ.
Complexes 7–9 were prepared by a similar procedure, the
quantities of reagents used and yields obtained are listed below.
[RuCl(tBu-saloxaz)(mes)] 3a. Complex 3a was prepared from
[RuCl2(mes)]2 (100 mg, 0.17 mmol), Bu-saloxaz (75 mg, 0.34
t
mmol) and NaOMe (25 mg, 0.47 mmol), in 46 mg yield, 28%.
Calc. for C22H28ClNO2Ru: C, 55.63; H, 5.94; N, 2.95. Found: C,
47.94; H, 5.88; N, 1.79%.(the complex appears to have lost
[Ru(4-Mepy)(iPr-saloxaz)(mes)][SbF6] 7. Complex 7 was
prepared from [RuCl(iPr-saloxaz)(mes)] (2a) (57 mg, 0.12
mmol), NaSbF6 (39 mg, 0.15 mmol) and 4-methylpyridine
(35 mg, 0.37 mmol) in 80 mg yield, 86%. Calc. for C27H33-
F6N2O2RuSb: C, 42.99; H, 4.41; N, 3.71. Found: C, 42.94; H,
1
ligand). H NMR δ 1.18 (s, 9H, CMe3), 2.19 (s, 9H, C6Me3),
4.33 (m, 2H, OCH ϩ OCHЈ), 4.65 (m, 1H, NCH ), 4.89 (s, 3H,
C6H3Me3), 6.38 (m, 1H, Ar-4-H ), 6.98 (dd, 1H, J 8.5, 1, Ar-6-
H ), 7.15 (m, 1H, Ar-5-H ), 7.47 (dd, 1H, J 8, 2, Ar-3-H ). MS
(FABϩ): m/z 441 [M Ϫ Cl]ϩ.
1
4.43; N, 3.81%. H NMR (400 MHz, CD2Cl2, 233 K) (isomer
ratio B : A = 85 : 15, data for A in square brackets) δ Ϫ0.05
[0.68] (d, 3H, J 7 Hz, CHMe2), 0.83 [1.06] (d, 3H, J 7 Hz,
CHMe2), 1.27 (m, 1H, CHMe2), 2.02 (s, 9H, C6Me3), 2.40 [2.32]
(s, 3H, 4-Mepy), 4.40 (m, 3H, OCH2 ϩ NCH ), 4.97 [5.02] (s,
3H, C6H3Me3), 6.52 [6.16] (m, 1H, Ar-4-H ), 6.99 [6.75] (m, 1H,
Ar-6-H ), 7.23 [7.07] (m, 1H, Ar-4-H ), 7.23 [7.10] (m, 2H,
py-3,5-H ), 7.43 [6.91] (m, 1H, Ar-3-H ) 8.55 [8.22] (m, 2H,
py-2,6-H ). MS (FABϩ): m/z 519 [M]ϩ and 426, [M-Mepy]ϩ.
[RuCl(tBu-saloxaz)(p-cymene)] 3b. Complex 3b was prepared
t
from [RuCl2(p-cymene)]2 (125 mg, 0.21 mmol), Bu-saloxaz
(94 mg, 0.43 mmol) and NaOMe (28 mg, 0.51 mmol), in 139 mg
1
yield, 70%. H NMR δ 1.17 (s, 9H, CMe3), 1.17, 1.24 (2 × d,
3H, J 7 Hz, CHMe2), 2.32 (s, 3H, Me), 2.77 (m, 1H, CHMe2),
4.35 (m, 2H, OCH ϩ OCHЈ), 4.69 (m, 1H, NCH ) 4.93 (d, 1H,
J 6, cymene) 5.34 (d, 1H, J 6, cymene), 5.40 (d, 1H, J 6,
cymene), 5.49 (d, 1H, J 6, cymene), 6.36 (t, 1H, J 7.5, Ar-4-H ),
6.93 (d, 1H, J 8.5, Ar-6-H ), 7.11 (t, 1H, J 8.5, Ar-5-H ),
7.38 (d, 1H, J 8, Ar-3-H ). MS (FABϩ): m/z 489 [M]ϩ and 454
[M Ϫ Cl]ϩ.
[Ru(2-Mepy)(iPr-saloxaz)(mes)][SbF6] 8. Complex 8 was
prepared from [RuCl(iPr-saloxaz)(mes)] (2a) (61 mg, 0.13
mmol), NaSbF6 (41 mg, 0.16 mmol) and 2-methylpyridine
(37 mg, 0.40 mmol) in 72 mg yield, 72%. Calc. for C27H33-
F6N2O2RuSb: C, 42.99; H, 4.41; N, 3.71. Found: C, 42.60; H,
1
4.18; N, 3.46%. H NMR (250 MHz, CD2Cl2) δ 0.65 (d, 3H,
[RuCl(Bz-saloxaz)(mes)] 4a. Complex 4a was prepared from
[RuCl2(mes)]2 (115 mg, 0.20 mmol), Bz-saloxaz (109 mg, 0.43
mmol) and NaOMe (27 mg, 0.49 mmol) in 141 mg yield, 71%.
Calc. for C25H26ClNO2Ruؒ0.5CH2Cl2: C, 55.54; H, 4.93; N,
2.54. Found: C, 55.90; H, 4.91; N, 2.47%. 1H NMR (400 MHz)
(isomer ratio B : A = 4 : 1, data for A in square brackets) δ 2.24
[2.16] (s, 9H, C6Me3), 2.78 [2.63] (dd, 1H, J 11, 14, CHPh), 3.96
[3.93] (dd, 1H, J 3.5, 14, CHЈPh), 4.35 [4.16 ϩ 4.35] (m, 2H,
OCH ϩ OCHЈ), 4.71 [4.58] (m, 1H, NCH ) 4.95 [4.89] (s, 3H,
C6H3Me3), 6.41 [6.50] (t, 1H, J 8, Ar-4-H ), 7.02 (d, 1H, J 8.5,
Ar-6-H ), 7.27 (m, 6H, Ar-5-H ϩ CH2Ph), 7.46 (dd, 1H, J 8, 2,
Ar-3-H ). MS (FABϩ): m/z 509 [M]ϩ and 474 [M Ϫ Cl]ϩ.
J 6.5, CHMe2), 1.10 (d, 3H, J 7, CHMe2), 2.13 (s, 9H, C6Me3),
2.50 (m, 1H, CHMe2), 2.84 (s, 3H, 2-Mepy), 4.51 (t, 1H, J 8.5
OCH ), 4.61 (m, 1H, OCHЈ), 4.72 (m, 1H, NCH ), 5.25 (s,
3H, C6H3Me3), 6.50 (t, 1H, J 7.5, Ar-4-H ), 7.05 (d, 1H, J 7.5
Ar-6-H ), 7.30 (m, 3H, Ar-3ϩ5-H, py-H ), 7.49 (d, 1H, J 7.5,
py-H), 7.99 (t, 1H, J 7, py-H ), 8.59 (d, 1H, J 5.5, py-6-H ). MS
(FABϩ): m/z 426, [M Ϫ (Me-py)]ϩ.
[Ru(PPh3)(iPr-saloxaz)(mes)][BPh4] 9. Complex 9 was pre-
pared from [RuCl(iPr-saloxaz)(mes)] (2a) (51 mg, 0.11 mmol),
NaBPh4 (45 mg, 0.13 mmol) and PPh3 (35 mg, 0.13 mmol) in
104 mg yield, 94%. Calc. for C63H61BNO2PRu: C, 75.14; H,
1
6.11; N, 1.39. Found: C, 74.38; H, 6.01; N, 1.35%. H NMR
[RuCl(Ph-saloxaz)(mes)] 5a. Complex 5a was prepared from
[RuCl2(mes)]2 (147 mg, 0.25 mmol), Ph-saloxaz (133 mg, 0.56
mmol) and NaOMe (34 mg, 0.63 mmol) in 185 mg yield, 76%.
Calc. for C24H24ClNO2Ru: C, 58.24; H, 4.89; N, 2.83. Found: C,
58.27; H, 4.76; N, 2.92%. 1H NMR (400 MHz, 233 K) (isomer
ratio A : B = 3 : 2, data for B in square brackets) δ 1.89 [2.01] (s,
9H, C6Me3), 4.10 [4.60] (s, 3H, C6H3Me3), 4.82 (m, 2H, OCH ϩ
OCHЈ), [4.20 ϩ 4.92] [2 × t, J 8.5, OCH ϩ OCHЈ], 5.51 [5.75] (t,
1H, J 10, NCH ), 6.60 [6.43] (t, 1H, J 7.5, Ar-4-H ), 6.99 [6.80]
(d, 1H, J 8, Ar-6-H ), 7.17 [7.18] (t, 1H, J 7.5, Ar-5-H ), 7.6 (br,
overlapping m, 6H, Ph ϩ Ar-3-H ). MS (FABϩ): m/z 495 [M]ϩ
and 460 [M Ϫ Cl]ϩ.
(CD2Cl2) (isomer ratio B : A = 1 : 1, data for A in square brack-
ets) δ 0.00 [0.92] (d, 3H, J 7, CHMe2), 0.58 [0.97] (d, 3H, J 7,
CHMe2), 1.21 [2.08] (m, 1H, CHMe2), 1.71 [1.68] (s, 9H,
C6Me3), 3.74 [3.20] (m, 1H, NCH ), 4.37 [2.87] (m, 1H, OCH ),
4.48 [5.06] (s, 3H, C6H3Me3), 4.53 [4.14] (m, 1H, OCHЈ), 6.51
[6.61] (m, 1H, Ar-4-H ), 6.80–7.90 (m, 38H, Ar-3,4,6-H ϩ PPh3
ϩ BPh4Ϫ). 31P-{1H} NMR δ 30.13 [30.90] MS (FABϩ): m/z 688,
[M]ϩ and 426, [M Ϫ PPh3]ϩ.
[Ru(solvent)(iPr-saloxaz)(mes)]SbF6. To
a
solution of
AgSbF6 (1.05 equivalents) in acetone (0.5 ml) was added a solu-
tion of [MCl(iPr-saloxaz)(mes)] (2a) (1.0 equivalents) in CH2Cl2
(4 ml), giving a yellow–orange solution and an immediate AgCl
precipitate. The solution was stirred for 1 h at room temper-
ature (protected from light) and was then filtered through Celite
(to remove AgCl). The solvent was evaporated, and the solid
was washed with chloroform to give an orange hygroscopic
[Ru(py)(iPr-saloxaz)(mes)][SbF6] 6. To
a
solution of
[RuCl(iPr-saloxaz)(mes)] (2a) (60 mg, 0.13 mmol) in MeOH
(10 ml) was added NaSbF6 (38 mg, 0.15 mmol) and pyridine
(43 mg, 0.54 mmol). The mixture was heated to reflux temper-
ature for 2 h with continuous stirring. On cooling a white
precipitate was observed. The solvent was evaporated and the
residue re-dissolved in CH2Cl2 prior to filtering through Celite.
The resulting red solution was evaporated to afford the crude
complex. Recrystallisation from CH2Cl2–ether (or CHCl3–
ether) gave 6 as a crystalline red–orange solid in 66 mg yield,
70%. Calc. for C26H31F6N2O2RuSb: C, 42.18; H, 4.22; N, 3.78.
Found: C, 41.79; H, 4.12; N, 3.35%. 1H NMR (CD2Cl2, 253 K)
(isomer ratio B : A = 84 : 16, data for A in square brackets)
δ Ϫ0.09 [0.74] (d, 3H, J 7 Hz, CHMe2), 0.87 [1.11] (d, 3H, J 7
Hz, CHMe2), 1.36 [2.41] (m, 1H, CHMe2), 2.07 (s, 9H, C6Me3),
4.47 (m, 2H, OCH ϩ OCHЈ), 4.56 [4.72] (m, 1H, NCH ), 5.10
(s, 3H, C6H3Me3), 6.58 [6.22] (t, 1H, J 7.5, Ar-4-H ), 7.06 [6.85]
(d, 1H, J 8, Ar-6-H ), 7.30 [6.98] (m, 1H, Ar-5-H ), 7.52 (m, 3H,
1
solid. This was then used for further reactions. H NMR (400
MHz CD2Cl2) δ 0.557, 1.20, (2 × d, 3H, J 7, CHMe2), 2.25 (s,
9H, C6Me3), 2.66 (m, 1H, CHMe2), 4.69 (m, 2H, OCH2), 5.00
(m, 1H, NCH ), 5.51 (s, 3H, C6H3Me3), 6.83 (t, 1H, J 8, Ar-4-
H ), 7.28 (d, 1H, J 8, Ar-6-H ), 7.44 (t, 1H, J 8, Ar-5-H ), 7.59 (d,
1H, J 8, Ar-3-H ). MS (FABϩ): 426, [M Ϫ solvent]ϩ.
Synthesis of [RuBr(iPr-saloxaz)(mes)] 10. A solution of
AgSbF6 (50 mg, 0.15 mmol) in acetone (0.5 ml) was added to a
solution of [RuCl(iPr-saloxaz)(mes)] (2a) (64 mg, 0.14 mmol) in
CH2Cl2 (4 ml), giving a yellow–orange solution and an immedi-
ate precipitate of AgCl. The solution was stirred for one hour at
room temperature (protected from light) and was then filtered
through Celite (to remove AgCl). The solvent was evaporated,
D a l t o n T r a n s . , 2 0 0 4 , 1 4 8 1 – 1 4 9 2
1489