Organometallics
Article
2-allyl-4-bromophenol, 2-allyl-4-nitrophenol, 2-allyl-6-phenylphenol,
and 2-allyl-6-methoxyphenol were prepared from the correspond-
ing ethers by a Claisen rearrangement.30 The potassium salts of these
2-allylphenol analogues were prepared by the reaction of the corres-
ponding 2-allylphenol and potassium methoxide.
7.63 (dd, 3JH−H = 8 Hz, 4JH−H = 2 Hz, 1H, C6H3), 7.77 (d, 3JH−H = 7.3
Hz, 1H, 4-Ph), 7.7−7.9 (m, 6H, o-PPh3). 31P{1H} NMR (162 MHz,
C6D6): δ 48.78 (s). Anal. Calcd for C38H33OPRu·0.4C6H14·0.1C6H8·
0.3H2O: C, 72.21; H, 5.59. Found: C, 72.02; H, 5.37. IR (KBr, cm−1):
1597 (w, νCC).
1H and 31P{1H} NMR spectra were measured on a JEOL LA300 or
a JEOL ECX400P spectrometer. The IR spectra were measured on a
JASCO FT/IR410 or FT/IR4100 spectrometer. UV−vis spectra were
measured on a Shimadzu UVSpec-1500 instrument. Elemental analyses
were performed on a Perkin-Elmer 2400 Series II CHN analyzer. The
compounds without elemental analyses were characterized by spectroscopic
methods.
RuCp[OC6H3(CH2CHCH2-2)(Br-4)-κ1O,η2C,C′](PPh3) (2e). Red
crystals, 27% yield. 1H NMR (400 MHz, C6D6): δ 1.62 (br dd,
2JH−H = 13 Hz, 3JH−H = 11 Hz, 1H, benzylic CHH), 2.69 (dd, 3JH−H
=
3
2
13.5 Hz, JH−P = 11.2 Hz, 1H, CHH), 2.87 (br dd, JH−H = 13 Hz,
3
3JH−H = 4 Hz, 1H, benzylic CHH), 3.13 (d, JH−H = 7.8 Hz, 1H,
3
CHH), 3.99 (s, 5H, Cp), 5.39 (m, 1H, CH−), 6.91 (d, JH−H
=
=
8.2 Hz, 1H, C6H3), 6.9−7.1 (m, 9H, m- and p-PPh3), 7.34 (d, 4JH−H
RuCp[OC6H4(CH2CHCH2-2)-κ1O](PPh3)2 (1a) and RuCp-
[OC6H4(CH2CHCH2-2)-κ1O,η2C,C′](PPh3) (2a). As a typical ex-
ample, treatment of RuCpCl(PPh3)2 with potassium 2-allylphenoxide
is described in detail. RuCpCl(PPh3)2 (186.9 mg, 0.2574 mmol) was
dissolved in THF (4 mL) in a Schlenk tube. A THF solution (5 mL)
of potassium 2-allylphenoxide (295.0 mg, 1.713 mmol) was added to
the solution, and the reaction mixture was warmed to 50 °C for 2 h.
After removal of all volatile materials, the resulting solid was extracted
with benzene and the benzene solution was evaporated to dryness.
The solid was recrystallized from cold Et2O to give red crystals of 1a in
75.8% yield (160.8 mg, 0.1952 mmol). IR (KBr, cm−1): 3051 (m),
2985(w), 2869 (w), 1957 (vw), 1894 (vw), 1823 (vw), 1634 (w),
1584 (s), 1479 (s), 1469 (s), 1443 (s), 1281 (s), 1088 (m), 741 (s),
695 (s), 529 (s), 516 (s). Anal. Calcd for C50H44OP2Ru: C, 72.89; H,
5.38. Found: C, 72.93; H, 5.14. Complex 1a constitutes an equilibrium
mixture with the mono(phosphine) complex 2a in a benzene solution.
3
4
2.8 Hz, 1H, C6H3), 7.39 (dd, JH−H = 8.2 Hz, JH−H = 2.8 Hz, 1H,
C6H3), 7.6−7.8 (m, 6H, o-PPh3). 31P{1H} NMR (162 MHz, C6D6): δ
48.62 (s). Anal. Calcd for C38H33OPRu·0.3H2O: C, 59.50; H, 4.46.
Found: C, 59.94; H, 4.50. IR (KBr, cm−1): 1573 (w, νCC).
RuCp[OC6H3(CH2CHCH2-2)(NO2-4)-κ1O:η2C,C′](PPh3) (2f). Red
crystals, 27% yield. 1H NMR (300 MHz, C6D6): δ 1.36 (br dd, 2JH−H
=
13 Hz, 3JH−H = 12 Hz, 1H, benzylic CHH), 2.56 (dd, 3JH−H = 13.5 Hz,
2
3
3JH−P =11.1 Hz, 1H, CHH), 2.80 (br dd, JH−H = 13 Hz, JH−H = 3
3
Hz, 1H, benzylic CHH), 3.02 (d, JH−H = 8.1 Hz, 1H, CHH), 3.83
3
(s, 5H, Cp), 5.26 (m, 1H, CH−), 6.71 (d, JH−H = 8.7 Hz, 1H,
C6H3), 7.0 (m, 9H, m- and p-PPh3), 7.6 (m, 6H, o-PPh3), 8.21 (d,
4JH−H = 3.0 Hz, 1H, C6H3), 8.34 (dd, 3JH−H = 8.9 Hz, 4JH−H = 2.9 Hz,
1H, C6H3). 31P{1H} NMR (122 MHz, C6D6): δ 49.1 (s). Anal. Calcd
for C32H28NO3PRu: C, 63.36; H, 4.65; N, 2.31. Found: C, 63.87; H,
4.84; N, 2.39. IR (KBr, cm−1): 1590 (m, νCC).
RuCp[OC6H3(CH2CHCH2-2)(OMe-6)-κ1O:η2C,C′](PPh3)
1
3
1a: H NMR (300 MHz, C6D6, 30.0 °C) δ 3.03 (d, JH−H = 6.9 Hz,
1
(2g). Red crystals, 63% yield. H NMR (400 MHz, C6D6): δ 1.97
3
2H, benzylic CH2), 4.21 (s, 5H, Cp), 5.04 (d, JH−H = 9.9 Hz, 1H,
2
3
3
3
(br dd, JH−H = 12 Hz, JH−H = 9 Hz, 1H, benzylic CHH), 2.83 (dd,
CH2), 5.06 (d, JH−H = 16.5 Hz, 1H, CH2), 6.11 (ddt, JH−H
=
3
3
3JH−H = 13.3 Hz, 3JH−P = 11.0 Hz, 1H, CHH), 3.11 (br dd, 2JH−H
=
16.5, JH−H = 9.9, JH−H = 6.9 Hz, 1H, CH), 7.6 (m, 6H, PPh3),
12 Hz, 3JH−H = 3 Hz, 1H, benzylic CHH), 3.21 (d, 3JH−H = 8.1 Hz, 1H,
CHH), 3.74 (s, 3H, 6-OMe), 3.83 (s, 5H, Cp), 5.61 (m, 1H,
other aromatic resonances obscured by other aromatic protons
1
assignable to the major species 3c and liberated PPh3. 2a: H NMR
3
(300 MHz, C6D6, 18.0 °C) δ 1.84 (dd, 2JH−H = 12.0, 3JH−H = 11.7 Hz,
CH−), 6.69 (t, JH−H = 7.2 Hz, 1H, C6H3), 6.8−7.2 (m, 11H, m- and
p-PPh3, C6H3), 7.8−7.9 (m, 6H, o-PPh3). 31P{1H} NMR (162 MHz,
C6D6): δ 47.4 (s). Anal. Calcd for C33H31O2PRu: C, 66.99; H, 5.28.
Found: C, 66.26; H, 5.92. IR (KBr, cm−1): 1584 (m, νCC).
RuCp[OC6H3(CH2CHCH2-2)(Me-6)-κ1O:η2C,C′](PPh3) (2h). Red
3
3
1H, benzylic CHH), 2.78 (dd, JH−H = 13.8, JH−P = 10.8 Hz, 1H,
2
3
CH2), 3.14 (br dd, JH−H = 12, JH−H = 4 Hz, 1H, benzylic CHH),
3
3.20 (d, JH−H = 7.8 Hz, 1H, CH2), 3.96 (s, 5H, Cp), 5.59 (m,
1H, CH−), 6.81 (td, 3JH−H = 7.5, 4JH−H = 1.2 Hz, 1H, 4-C6H4), 6.9
(br.m, 1H, C6H4), 7.0 (m, 9H, m- and p-PPh3), 7.26 (t, 3JH−H = 8 Hz,
2H, C6H4), 7.8 (m, 6H, o-PPh3); 31P{1H} NMR (122 MHz, C6D6) δ
48.97 (s).
crystals, 37% yield. 1H NMR (300 MHz, C6D6): δ 1.86 (br dd, 2JH−H
=
3
13 Hz, JH−H = 11 Hz, 1H, benzylic CHH), 2.61 (s, 3H, 6-Me), 2.78
3
3
(dd, JH−H = 14.0 Hz, JH−P = 11.0 Hz, 1H, CHH), 3.19 (br dd,
2JH−H = 13 Hz, 3JH−H = 4 Hz, 1H, benzylic CHH), 3.22 (d, 3JH−H = 7.8
Hz, 1H, CHH), 3.99 (s, 5H, Cp), 5.64 (m, 1H, CH−), 6.79 (t,
3JH−H = 7.2 Hz, 1H, C6H3), 7.0 (m, 9H, m- and p-PPh3), 7.22 (d,
RuCp[OC6H3(CH2CHCH2-2)(OMe-4)-κ1O,η2C,C′](PPh3)
(2b). Red crystals, 33% yield. 1H NMR (400 MHz, C6D6): δ 1.90 (br
2
3
dd, JH−H = 12 Hz, JH−H = 11 Hz, 1H, benzylic CHH), 2.78 (dd,
3JH−H = 13.7 Hz, 3JH−P = 11.0 Hz, 1H, CHH), 3.11 (br dd, 2JH−H
=
3JH−H = 7.2 Hz, 1H, C6H3), 7.30 (d, JH−H = 7.2 Hz, 1H, C6H3), 7.8
3
12 Hz, 3JH−H =3 Hz, 1H, benzylic CHH), 3.21 (d, 3JH−H = 8.2 Hz, 1H,
CHH), 3.61 (s, 3H, 4-OMe), 3.99 (s, 5H, Cp), 5.56 (m, 1H, CH-),
6.9−7.2 (m, 12H, m- and p-PPh3, C6H3), 7.8−7.9 (m, 6H, o-PPh3).
31P{1H} NMR (162 MHz, C6D6): δ 48.63 (s). IR (KBr, cm−1): 1573
(m, νCC).
(m, 6H, o-PPh3). 31P{1H} NMR (122 MHz, C6D6): δ 50.0 (s). Anal.
Calcd for C33H31OPRu: C, 68.85; H, 5.43. Found: C, 68.89; H, 6.16.
IR (KBr, cm−1): 1587 (m, νCC).
RuCp[OC6H3(CH2CHCH2-2)(Ph-6)-κ1O:η2C,C′](PPh3) (2i). Red
crystals, 64% yield. 1H NMR (400 MHz, C6D6): δ 1.85 (br dd,
RuCp[OC6H3(CH2CHCH2-2)(Me-4)-κ1O,η2C,C′](PPh3) (2c). Red
2JH−H = 12 Hz, 3JH−H = 11 Hz, 1H, benzylic CHH), 2.82 (dd, 3JH−H
=
needles, 28% yield. 1H NMR (400 MHz, C6D6): δ 1.88 (br dd, 2JH−H
=
14.2 Hz, 3JH−P = 11.0 Hz, 1H, CHH), 3.04 (d, 3JH−H = 8.2 Hz, 1H,
3
2
3
12 Hz, JH−H = 12 Hz, 1H, benzylic CHH), 2.42 (s, 3H, 4-Me), 2.80
CHH), 3.11 (br dd, JH−H = 13 Hz, JH−H = 4 Hz, 1H, benzylic
3
3
3
(dd, JH−H = 13.7 Hz, JH−P = 11.0 Hz, 1H, CHH), 3.12 (br dd,
2JH−H = 13 Hz, 3JH−H = 4 Hz, 1H, benzylic CHH), 3.24 (d, 3JH−H = 7.8
Hz, 1H, CHH), 3.98 (s, 5H, Cp), 5.61 (m, 1H, CH-), 6.9−7.1
(m, 9H, m- and p-PPh3), 7.07 (d, 4JH−H = 1.8 Hz, 1H, C6H3), 7.13 (dd,
CHH), 3.85 (s, 5H, Cp), 5.51 (m, 1H, CH−), 6.81 (t, JH−H = 7.3
Hz, 1H, C6H3), 7.0−7.1 (m, 9H, m- and p-PPh3), 7.23 (br dd, 3JH−H
=
4
3
7 Hz, JH−H = 1 Hz, 1H, C6H3), 7.29 (t, JH−H = 7.4 Hz, 1H, 6-Ph),
7.40 (t, 3JH−H = 7.6 Hz, 2H, 6-Ph), 7.45 (br dd, 3JH−H = 7 Hz, 4JH−H
=
3JH−H = 8.0 Hz, JH−H = 2.0 Hz, 1H, C6H3), 7.18 (d, JH−H = 8.3 Hz,
1H, C6H3), 7.7−7.9 (m, 6H, o-PPh3). 31P{1H} NMR (162 MHz,
C6D6): δ 48.63 (s). Anal. Calcd for C33H31OPRu: C, 68.85; H, 5.43.
Found: C, 68.24; H, 5.94. IR (KBr, cm−1): 1571 (w, νCC).
4
3
3
1 Hz, 1H, C6H3), 7.6−7.8 (m, 6H, o-PPh3), 7.96 (d, JH−H = 7.3 Hz,
2H, 6-Ph). 31P{1H} NMR (162 MHz, C6D6): δ 50.01 (s). Anal. Calcd
for C38H33OPRu; C, 71.57; H, 5.22. Found: C, 71.78; H, 5.17. IR
(KBr, cm−1): 1583 (m, νCC).
RuCp[OC6H3(CH2CHCH2-2)(Ph-4)-κ1O,η2C,C′](PPh3) (2d). Red
van’t Hoff Plot for Equilibrium between 1a and 2a. Complex
1a (12.5 mg, 0.0152 mmol) was dissolved in benzene-d6 (442.6 mL).
In the NMR tube a flame-sealed capillary containing a benzene-d6
solution of PMe2Ph was added as an internal standard. The temperature
was changed in the range (25.0 − 60.0) 0.1 °C, and the concentration
of each species was estimated by the 31P{1H} NMR spectra. The
equilibrium constant K1 was defined as K1 = [2a][PPh3]/[1a]. Before this
experiment, the suitable pulse delay for this experiment was determined to
crystals, 45% yield. 1H NMR (400 MHz, C6D6): δ 1.86 (br dd, 2JH−H
=
3
3
13 Hz, JH−H = 11 Hz, 1H, benzylic CHH), 2.79 (dd, JH−H = 14 Hz,
3JH−P = 11 Hz, 1H, CHH), 3.18 (br dd, JH−H = 13 Hz, JH−H = 4
2
3
3
Hz, 1H, benzylic CHH), 3.22 (d, JH−H = 8.3 Hz, 1H, CHH), 3.98
(s, 5H, Cp), 5.60 (m, 1H, CH−), 6.9−7.1 (m, 9H, m- and p-PPh3),
7.26 (d, 3JH−H = 8 Hz, 1H, C6H3), 7.13 (t, 3JH−H = 7.3 Hz, 1H, 4-Ph),
7.31 (t, 3JH−H = 7.3 Hz, 2H, 4-Ph), 7.58 (d, 1H, 3JH−H = 2 Hz, C6H3),
390
dx.doi.org/10.1021/om200974c | Organometallics 2012, 31, 381−393