Organometallics
Article
2
8
H, ArH, J = 6.04 Hz). Anal. Calcd for C H F O PRu: C, 59.91; H,
.88. Found: C, 59.90; H, 9.01. (d) [Ru(Cp){η -1,2,3-
and the solution was stored at −40 °C. The desired compound
47
83
6
3
6
1
precipitated as a white solid (160 mg, 67% yield). H NMR (400
C H (OC H ) }][PF ] ([1-C18][PF ]): Under a nitrogen atmos-
MHz, CD CN): δ = 0.91(t, 9H, CH , J = 6.90 Hz), 1.23−1.72 (m,
6
3
18 37
3
6
6
3
3
phere, [Ru(Cp)(NCCH ) ][PF ] (100 mg, 0.226 mmol) and 1,2,3-
24H, CH ), 3.90 (t, 6H, ArOCH , J = 6.42 Hz), 5.18 (s, 5H, Cp), 5.99
3
3
6
2
2
tris(octadecyloxy)benzene (300 mg, 0.340 mmol) were dissolved in
(s, 3H, ArH). Anal. Calcd for C H F O PRu: C, 50.50; H, 6.87.
29 47 6 3
6
acetonitrile (1 mL), and the reaction mixture was heated at 90 °C for
Found: C, 50.70; H, 6.70. (b) [Ru(Cp){η -1,3,5-C H (OC H ) }]-
6 3 12 25 3
43 h under stirring. Acetonitrile was added to the reaction mixture and
[PF ] ([2-C12][PF ]): This compound was synthesized as described
6 6
heated, and the supernatant was removed by decantation. Recrystal-
for [1-C6][PF ] using [Ru(Cp)(NCCH ) ][PF ] (138 mg, 0.32
6 3 3 6
lization of the precipitate from methanol (−40 °C) afforded the
mmol), 1,3,5-tris(dodecyloxy)benzene (205 mg, 0.32 mmol), and
acetonitrile (2 mL). Acetonitrile was added to the crude product, and
the solution was washed three times with hexane. After evaporating
acetonitrile and drying under vacuum at 80 °C for 15 h, the desired
compound was obtained as a pale yellow liquid (148 mg, yield 48%).
The liquid crystallized when left at room temperature after cooling to
1
desired compound as a white solid (216 mg, 80% yield). H NMR
(
(
6
400 MHz, CDCl ): δ = 0.88 (t, 9H, CH , J = 6.82 Hz), 1.26−1.79
3
3
m, 96H, CH ), 3.82 (m, 2H, ArOCH ), 3.96 (t, 2H, ArOCH , J =
2
2
2
.34 Hz), 4.09 (m, 2H, ArOCH ), 5.25 (s, 5H, (Cp)), 5.85 (t, 1H,
2
ArH, J = 6.04 Hz), 6.00 (d, 2H, ArH, J = 5.92 Hz). Anal. Calcd for
1
C H F O PRu: C, 65.35; H, 10.04. Found: C, 65.32; H, 10.17.
−40 °C. H NMR (400 MHz, CDCl ): δ = 0.88 (t, 9H, CH , J = 6.84
6
3
119
6
3
3
3
6
Synthesis of [Ru(Cp){η -1,2,3-C H (OC H ) }][FSA] ([1-Cn]-
Hz), 1.26−1.75 (m, 60H, CH ), 3.97 (t, 6H, ArOCH , J = 5.82 Hz),
6
3
n
2n+1 3
2
2
6
[
[
FSA]). (a) [Ru(Cp){η -1,2,3-C H (OC H ) }][FSA] ([1-C2]-
FSA]): [Ru(Cp){η -1,2,3-C H (OC H ) }][PF ] (30.8 mg, 0.059
5.20 (s, 5H, Cp), 5.98 (s, 3H, ArH). Anal. Calcd for C H F O PRu:
6
3
2
5
3
47 83 6 3
6
6
6
3
2
5
3
6
C, 59.91; H, 8.88. Found: C, 59.66; H, 8.95. (c) [Ru(Cp){η -1,3,5-
C H (OC H ) }][PF ] ([2-C18][PF ]): This compound was
mmol) was dissolved in a mixture of water and acetone. An aqueous
solution of K[FSA] (25.1 mg, 0.141 mmol) was added to this solution
and stirred. After the removal of acetone by evaporation, the resulting
suspension was extracted 10 times with dichloromethane. The product
was dissolved in a small amount of acetone, and diethyl ether was
6
3
18 37
3
6
6
synthesized as described for [1-C6][PF ] using [Ru(Cp)(NCCH ) ]-
6
3 3
[PF ] (155 mg, 0.35 mmol), 1,3,5-tris(octadecyloxy)benzene (332 mg,
6
0.37 mmol), and acetonitrile (1 mL). The product was purified by
column chromatography (activated alumina; eluent, toluene and then
dichloromethane/THF (1:1, v/v)). Recrystallization from methanol
(−40 °C) afforded the desired compound as a white solid (342 mg,
added. The desired compound precipitated as a white solid (28 mg,
1
8
3
2
5% yield). H NMR (400 MHz, CD CN): δ = 1.37 (m, 9H, CH ),
3
3
1
.85 (m, 2H, ArOCH ), 4.03 (q, 2H, ArOCH , J = 7.13 Hz), 4.13 (m,
82% yield). H NMR (400 MHz, CDCl ): δ = 0.88 (t, 9H, CH , J =
2
2
3
3
H, ArOCH ), 5.28 (s, 5H, Cp), 5.66 (t, 1H, ArH, J = 5.88 Hz), 5.84
6.84 Hz), 1.25−1.73 (m, 96H, CH ), 3.97 (t, 6H, ArOCH , J = 6.16
2
2
2
(
d, 2H, ArH, J = 5.96 Hz). Anal. Calcd for C H F NO RuS : C,
Hz), 5.20 (s, 5H, Cp), 5.97 (s, 3H, ArH). Anal. Calcd for
C H F O PRu: C, 65.35; H, 10.04. Found: C, 65.57; H, 10.42.
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23
2
7
2
3
6.69; H, 4.17; N, 2.52. Found: C, 36.92; H, 4.37; N, 2.25. (b)
6
3
119
6
3
6
6
[
Ru(Cp){η -1,2,3-C H (OC H ) }][FSA] ([1-C6][FSA]): [Ru(Cp)-
Synthesis of [Ru(Cp){η -1,3,5-C H (OC H ) }][FSA] ([2-Cn]-
6
3
6
13
3
6
3
n
H
2n+1 3
) }][FSA] ([2-C6]-
13 3
6
6
{
η -1,2,3-C H (OC H ) }][PF ] (36.5 mg, 0.052 mmol) was
[FSA]). (a) [Ru(Cp){η -1,3,5-C
6
H
3
(OC
6
6
3
6
13
3
6
dissolved in a mixture of water and acetone. An aqueous solution of
K[FSA] (40.2 mg, 0.23 mmol) was added to this solution and stirred.
After the removal of acetone by evaporation, the resulting suspension
was extracted 10 times with dichloromethane. The product was dried
under vacuum at 80 °C for 15 h to afford a colorless liquid (30 mg,
[FSA]): This compound was synthesized as described for [1-
6
C6]FSA using [Ru(Cp){η -1,3,5-C H (OC18H ) }][PF ] (214.0
6 3 37 3 6
mg, 0.31 mmol) and K[FSA] (131.1 mg, 0.73 mmol). The desired
compound was obtained as a pale yellow liquid (143.1 mg, 64% yield).
1
H NMR (400 MHz, CDCl ) δ = 0.91 (t, 9H, CH , J = 6.88 Hz),
3
3
8
0% yield). This salt was a liquid after vacuum drying; however, it
1.30−1.77 (m, 24H, CH ), 3.94 (t, 6H, ArOCH , J = 6.26 Hz), 5.21 (s,
2
2
solidified as a white solid when stored overnight in a refrigerator (6
5H, Cp), 5.98 (s, 3H, ArH). Anal. Calcd for C H F NO RuS : C,
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47
2
7
2
1
°
C). H NMR (400 MHz, CD CN): δ = 0.92 (m, 9H, CH ), 1.32−
48.05; H, 6.54; N, 1.93. Found: C, 48.50; H, 6.59 N, 2.01. (b)
3
3
6
1
.79 (m, 24H, CH ), 3.74 (m, 2H, ArOCH ), 3.96 (t, 2H, ArOCH , J
[Ru(Cp){η -1,3,5-C H (OC H ) }][FSA] ([2-C12][FSA]): This
2
2
2
6
3
12 25 3
=
6.24 Hz), 4.08 (m, 2H, ArOCH ), 5.25 (s, 5H, Cp), 5.65 (t, 1H,
compound was synthesized as described for [1-C6]FSA using
2
6
ArH, J = 6.12 Hz), 5.84 (d, 2H, ArH, J = 6.12 Hz). Anal. Calcd for
[Ru(Cp){η -1,3,5-C H (OC H ) }][PF ] (63.0 mg, 0.067 mmol)
6
3
12 25
3
6
C H F NO RuS : C, 48.05; H, 6.54; N, 1.93. Found: C, 47.73; H,
and K[FSA] (26.6 mg, 0.15 mmol). The desired compound was
obtained as a colorless liquid (41.3 mg, 63% yield). H NMR (400
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47
2
7
2
6
1
6
.60; N, 1.91. (c) [Ru(Cp){η -1,2,3-C H (OC H ) }][FSA] ([1-
6
3
12 25 3
C12][FSA]): This compound was synthesized as described for [1-
MHz, CDCl ): δ = 0.88 (t, 9H, CH , J = 6.84 Hz), 1.26−1.74 (m,
3
3
6
C6]FSA using [Ru(Cp){η -1,2,3-C H (OC H ) }][PF ] (78 mg,
96H, CH ), 3.95 (t, 6H, ArOCH , J = 6.16 Hz), 5.20 (s, 5H, Cp), 5.98
6
3
12 25
3
6
2
2
0
.082 mmol) and K[FSA] (40 mg, 0.22 mmol). The desired
(s, 3H, ArH). Anal. Calcd for C H F NO RuS : C, 57.76; H, 8.56;
47 83 2 7 2
N, 1.43. Found: C, 58.06; H, 8.76; N, 1.46. (c) [Ru(Cp){η -1,3,5-
6
compound was obtained as a colorless liquid (54 mg, 67% yield).
1
H NMR (400 MHz, CDCl ): δ = 0.88 (t, 9H, CH , J = 6.56 Hz),
C H (OC H ) }][FSA] ([2-C18][FSA]): This compound was
3
3
6
3
18 37 3
6
1
.27−1.78 (m, 60H, CH ), 3.83 (m, 2H, ArOCH ), 3.96 (t, 2H,
synthesized as described for [1-C6]FSA using [Ru(Cp){η -1,3,5-
}][PF ] (157 mg, 0.13 mmol) and K[FSA] (98 mg,
2
2
ArOCH , J = 6.32 Hz), 4.10 (m, 2H, ArOCH ), 5.26 (s, 5H, Cp), 5.86
C
6
H
3
(OC18
H
37
)
3
6
2
2
(
t, 1H, ArH, J = 5.92 Hz), 5.99 (d, 2H, ArH, J = 5.96 Hz). Anal. Calcd
0.54 mmol). The product was further purified by gel permeation
chromatography (Japan Analytical Industry LC-908, eluent: chloro-
form) and recrystallized from methanol (−40 °C). The desired
for C H F NO RuS : C, 57.76; H, 8.56; N, 1.43. Found: C, 58.10;
H, 8.62; N, 1.45. (d) [Ru(Cp){η -1,2,3-C H (OC H ) }][FSA] ([1-
C18][FSA]): This compound was synthesized as described for [1-
C6]FSA using [Ru(Cp){η -1,2,3-C H (OC H ) }][PF ] (100 mg,
47
83
2
7
2
6
6
3
18 37 3
1
compound was obtained as a white solid (116 mg, 72% yield). H
6
NMR (400 MHz, CDCl
1.74 (m, 96H, CH ), 3.95 (t, 6H, ArOCH
Cp), 5.98 (s, 3H, ArH). Anal. Calcd for C63
H, 9.75; N, 1.14. Found: C, 63.98; H, 10.05; N, 1.15.
X-ray Crystallography. The single crystals of [1-C2][X] (X = PF
6
): δ = 0.88 (t, 9H, CH
, J = 6.16 Hz), 5.20 (s, 5H,
NO RuS : C, 63.48;
, J = 6.84 Hz), 1.26−
6
3
18 37
3
6
3
3
0
.084 mmol) and K[FSA] (39.6 mg, 0.22 mmol). Recrystallization of
2
2
the product from methanol (−40 °C) furnished the desired compound
as a white solid (69.8 mg, 68% yield). H NMR (400 MHz, CDCl ): δ
=
2
ArOCH ), 5.26 (s, 5H, Cp), 5.96 (m, 3H, ArH). Anal. Calcd for
C H F NO RuS : C, 63.48; H, 9.75; N, 1.14. Found: C, 63.60; H,
1
H
119
F
2
7
2
1
3
0.88 (t, 9H, CH , J = 6.86 Hz), 1.26−1.80 (m, 96H, CH ), 3.81 (m,
3
2
H, ArOCH ), 3.97 (t, 2H, ArOCH , J = 6.30 Hz), 4.09 (m, 2H,
and FSA) were grown by the slow diffusion of diethyl ether into the
concentrated solutions of the salts in acetone. The single crystals of [1-
2
2
2
C6][PF
methanol solutions. The single crystals of [1-C18][PF
6
] and [1-C12][PF
] were grown by the slow evaporation of
63
119
2
7
2
6
6
0.00; N, 1.13.
] were grown
6
Synthesis of [Ru(Cp){η -1,3,5-C H (OC H ) }][PF ] ([2-Cn]-
6 6 3 6 13 3 6 6
by the slow evaporation of ethanol solutions. X-ray diffraction data
were collected using a Bruker APEX II Ultra CCD diffractometer using
MoKα radiation (λ = 0.71073 Å). All the calculations were performed
6
3
n
2n+1 3
6
6
[PF ]). (a) [Ru(Cp){η -1,3,5-C H (OC H ) }][PF ] ([2-C6][PF ]):
This compound was synthesized as described for [1-C6][PF ] using
6
2
4
[
Ru(Cp)(NCCH ) ][PF ] (149 mg, 0.46 mmol), 1,3,5-tris(hexyloxy)-
using SHELXTL. The structures were determined by the direct
3
3
6
benzene (140 mg, 0.47 mmol), and acetonitrile (1 mL). The product
was dissolved in a small amount of ethyl acetate, hexane was added,
methods (SHELXS 97). All of the nonhydrogen atoms were refined
anisotropically. ORTEP-3 for Windows was used to produce the
2
5
1
284
Organometallics 2015, 34, 1279−1286