A R T I C L E S
Agapie et al.
1H NMR spectroscopy in CDCl
was absent by both analytical methods. 9,10-Dimethylphenanthrene was
identified as the major product by H NMR spectroscopy in CDCl
and GC-MS.
and GC-MS. Hexamethyl benzene
Subsequently, the reaction mixture was cooled in a dry ice/acetone bath
and degassed. Following removal of ethylene, the mixture was allowed
to warm to room temperature, and volatile materials were vacuum
transferred to a J-Young tube and analyzed by 1H and C NMR
spectroscopy. Isotope effects obtained from the ratio of the integrals
3
1
3
13
Trimerization of a C
NaB[C (CF . Dichloromethane-d
J-Young tube charged with 1 (9.2 mg, 11.4 µmol, 1 equiv) and NaB-
(CF (12.2 mg, 13.8 µmol, 1.2 equiv). The mixture was
warmed up to room temperature using a water bath, followed by mixing
via mechanical rotation) for 10 min. The mixture turned brown upon
the starting materials dissolving. A 1:1 mixture of C and C (128.2
2
D
4
/C
2
H
4
Mixture with 1 Activated with
6
H
3
) ]
3 2 4
2
was vacuum transferred to a
corresponding to the olefinic peaks: 3.1, 3.2, 3.1 (298 K, cis-C
4.0, 4.1 (298 K, trans-C ), 1.3, 1.3 (298 K, gem-C
3.4 (273 K, cis-C ), 3.6, 3.6 (248 K, cis-C ). Ratios of the
methyl integral versus the smallest olefinic peak integral: 7.7, 8.8, 7.7
(298 K, cis-C ), 9.2, 9.2 (298 K, trans-C ), 5.0, 4.9 (298 K,
gem-C ). The solid residue was partitioned between water and
dichloromethane, and the organic fraction was analyzed by GC-MS
to reveal the presence of d -o-vinylbiphenyl and biphenyl. See the
2 2 2
H D
),
2 2
H
D
2
H D ), 4.0,
2 2 2
[C H
6 3
3
)
2
]
4
H
2 2
D
2
2 2 2
H D
(
2
H
2
D
2
2 2 2
H D
D
2 4
H
2 4
2 2 2
H D
mL at 29 torr, 200 µmol, 17.5 equiv) was condensed in (∼2.4 atm in
the tube at room temperature). The reaction mixture was allowed to
mix for 1 h at room temperature during which time it achieved a brown-
green color. The reaction vessel was cooled in a dry ice/acetone bath
and degassed. Following removal of ethylene, the mixture was allowed
to reach room temperature and volatile materials were vacuum
transferred to a round-bottom flask and analyzed by GC-MS. The
2
1
Supporting Information for H NMR spectra of the olefin region of
2
trimers resulted from different ethylene-d isotopomers and couplings
obtained from these spectra.
Reaction of 1 with Higher Olefins upon Halide Abstraction. These
experiments were performed with propylene, 1-butene, cis- and trans-
2-butene, and styrene. The following procedure is typical: Dichlo-
romethane (2 mL) was vacuum transferred to a Schlenk flask charged
1
-hexene fraction shows a 1:3:3:1 distribution of isotopomers (C
, C , and C 12). The solid residue was partitioned between
water and dichloromethane, and the organic fraction was analyzed by
6 12
H ,
C H D
6 8 4
H D
6 4 8
6
D
6 3 3 2 4
with 1 (37 mg, 46.0 µmol, 1 equiv) and NaB[C H (CF ) ] (49 mg,
GC-MS to reveal the presence of d
biphenyl.
0
- and d
4
-o-vinylbiphenyl and
55.3 µmol, 1.2 equiv). The mixture was warmed up to room temperature
using a water bath followed by magnetic stirring for 10 min. The
mixture turned brown upon the starting materials dissolving. Propylene
(128.2 mL at 160 torr, 1.1 mmol, 24.6 equiv) was condensed in. (In
the case of styrene, the olefin was added via syringe, in the glove-
box.) The reaction mixture was allowed to mix for 24 h at room
temperature during which the mixture turned green. Upon opening to
2 4 2 4
Trimerization of a C D /C H Mixture with 1 Activated with
MAO. Compound 1 (8.2 mg, 10.1 µmol, 1 equiv) was suspended in
toluene (30 mL), and the mixture was cooled to -78 °C in a dry ice/
acetone bath. Under counterflow of argon, the Teflon stopcock was
replaced with a rubber septum, and MAO solution (10% in toluene, d
2
-
-
)
0.875 g/mL, 2.4 mL, 300 equiv) was added via syringe. The septum
was replaced with the Teflon stopcock. The mixture was degassed
briefly and placed under 1:1 C /C
air, the reaction was quenched with 1 mL of aqueous CO
3
/HCO
3
solution. The mixture was transferred to a scintillation vial and
centrifuged. The organic layer was separated and filtered through silica
gel, then volatile materials were removed under vacuum. The residue
2
D
4
H
2 4
mixture (∼2.3 atm static
pressure, 10 mmol, 1000 equiv) while warming up to room temperature
in a water bath. The reaction mixture was allowed to stir for 1.5 h. An
aliquot was collected, the reaction was quenched with water, and the
mixture was analyzed by GC-MS. The 1-hexene fraction resolves in
was analyzed by NMR spectroscopy in CDCl
respect to diphosphine at the end of the reaction: 1H NMR (300 MHz,
CDCl ) δ: 2.65, 2.68 (two br singlets, 3H, NCH), 3.66, 3.73 (two br
singlets, 12H, OCH
(major, doublets, JPP ) 122 Hz), 19.2, 37.9 (minor, doublets, JPP ) 9
3
and GC-MS. With
3
31
a quartet showing a 1:3:3:1 distribution of isotopomers (C
, and C - and d -o-vinylbiphenyl do not resolve on the
GC trace but are both present according to the mass spectrum.
6 6 8 4
H12, C H D ,
3 3
). P NMR (121 MHz, CDCl ) δ: 29.6, 54.9
C
6
H D
4 8
6
D12). d
0
4
31
Hz). The same major peaks in P NMR spectrum are observed when
O4
/PNPO4
2 2 6 3 3 2 4
a solution (CH Cl ) of PNP and NaB[C H (CF ) ] (1.1 equiv) is
Trimerization of a C
Activated with MAO. A solution of CrCl
2
D
4
/C
2
H
4
Mixture with CrCl
(THF) (6 mg, 16 µmol, 1
(THF)
3 3
stirred for 36 h, then the reaction quenched with water. The nature of
the resulting biphenyl olefin was determined from the aliphatic and
3
3
equiv) in dichloromethane (1 mL) was added to a dichloromethane
solution (1 mL) of 1 (8.3 mg, 16 µmol, 1 equiv). The reaction mixture
was allowed to stir for 1 h at room temperature. Volatile materials
were removed in vacuo, and toluene (40 mL) was added. The resulting
mixture was cooled down in a dry ice/acetone bath, and the Teflon
stopcock was replaced with a rubber septum under counterflow of argon.
MAO solution (10% in toluene, d ) 0.875 g/mL, 3.2 mL, 300 equiv)
was added via syringe, then the septum was replaced with the Teflon
1
olefin peaks in the H NMR spectrum. 2-Vinyl-biphenyl, 2-(1-phenyl-
vinyl)-biphenyl, and 2-i-propenyl-biphenyl were identified using lit-
erature reports. The remaining of the biphenyl derivatives are presented
below.
2
-(1-i-Propyl-vinyl)-biphenyl. Obtained from 3-methyl-1-butene.
1
3
H NMR (500 MHz, CDCl
.95 (app h, JHH ) 6.8 Hz, 1H, CH(CH
3
) δ: 0.82 (d, JHH ) 6.8 Hz, 6H, CH
3
),
3
3
1
2
3
)
2
2
), 5.10 (dd, JHH ) 0.4 Hz,
3
J
HH ) 1.5 Hz, 1H, dCHH), 5.14 (app t, JHH ) JHH ) 1.5 Hz, 1H,
dCHH).
2-(1-Ethyl-vinyl)-biphenyl. Obtained from 1-butene. H NMR (500
MHz, CDCl
7.3 Hz, 2H, CH
Hz, 1H, dCHH).
stopcock. The mixture was degassed briefly and placed under 1:1 C
mixture (∼1.4 atm static pressure at room temperature, 1.4 mmol,
75 equiv) while warming up to room temperature in a water bath. It
2 4
D /
2 4
C H
8
1
3
3
was allowed to stir for 2.5 h; the mixture turned pale green. An aliquot
was collected, the reaction was quenched with water, and the mixture
was analyzed by GC-MS. The 1-hexene fraction displays a 1:3:3:1
3
) δ: 0.82 (d, JHH ) 7.3 Hz, 3H, CH
3
), 1.91 (q, JHH )
2
CH ), 5.08 (m, 1H, dCHH), 5.10 (app q, JHH ) 1.4
3
distribution of isotopomers (C
Trimerization of cis-, trans-, and gem-C
was vacuum transferred to a J-Young tube or Schlenk flask charged
with 1 (8-34 mg, 10-42 µmol, 1 equiv) and NaB[C (CF (10.5-
5 mg, 12-51 µmol, 1.2 equiv). The mixture was warmed up to room
temperature using a water bath followed by mixing (via mechanical
rotation for NMR tubes or magnetic stirring for flasks) for 10 min.
The mixture turned brown upon the starting materials dissolving.
Labeled ethylene (128.2 mL at 30-125 torr, 200-860 µmol, 17.5-23
equiv) was condensed in (∼2.3-3.8 atm in the vessel at room
temperature). The reaction mixture was allowed to mix for 1-1.5 h at
room temperature during which the mixture turned brown-green.
6
H
12, C
6
H
8
D
4
, C
6
H
4
D
8
, and C
6
D
12).
2-(E-1-Methyl-propenyl)-biphenyl. Obtained in the reaction with
trans-2-butene. 1H NMR (500 MHz, CDCl
) δ: 1.53 (app q, 3H,
)),
). NOE
2
H
2
D
2
. Dichloromethane-
3
dC(Ar)CH
5.55 (qq, 4
3
), 1.67 (dq, 5JHH ) 1.1, JHH ) 6.8 Hz, 1H, dCH(CH
3
3
d
2
H
3
)
3 2
]
4
J
HH ) 1.5 Hz, 3
J
HH ) 6.8 Hz, 1H, dCHCH
3
6
4
experiment: magnetization of the 1.53 ppm signal does not transfer to
the 5.55 ppm signal.
2-(Z-1-Methyl-propenyl)-biphenyl. Obtained in the reaction with
1
5
cis-2-butene. H NMR (500 MHz, CDCl
3
) δ: 1.43 (app d, JHH ) 1.2,
3
5
4
J
HH ) 6.7 Hz, 3H, dCHCH
3
), 1.73 (app q, JHH ≈ JHH ) 1.2 Hz, 1H,
4
3
C(Ar)CH
3
), 5.44 (app q, JHH ) 1.2 Hz, JHH ) 6.6 Hz, 1H, dCH(CH
3
)).
NOE experiment: magnetization of the 1.73 ppm signal transfers at
5.44 ppm signal.
14294 J. AM. CHEM. SOC.
9
VOL. 129, NO. 46, 2007