1
586 Organometallics, Vol. 17, No. 8, 1998
Burdeniuc and Crabtree
9
identical to that reported for perfluoro-1-methyl-1-
reported), -56.9 (CF3), -117.3 (CF2), -122.4 (CF2),
-136.8 (CF2); IR (NaCl neat film) obsd 3505 (N-H),
3345 (N-H), 1676 (CdC), 1611 (N-H), 1268 (C-F),
cyclohexene: 19F NMR δ obsd -136.3 (CF2, 2F), -136.2
(
(
(
(
CF2, 2F), -122.1 (CF2, 2F), -112.3 (CF, 1F), -112.0
9
-1
CF2, 2F), -61.1 (CF3, 3F); (lit. -136.4 (CF2), -135.9
1096 cm (C-F); lit. (medium not reported), 3450 (N-
-1
CF2), -121.3 (CF2), -115.4 (C-F), -110.9 (CF2), -61.3
CF3)).
H), 3270 (N-H), 1665 cm (CdC); UV(EtOH) obsd 275
1
3
(ꢀ ) 21 800), lit. 275 (ꢀ ) 5500); mp, obsd 99-100 °C,
1
3
A green residue, obtained on removal of the volatile
lit. 101 °C.
fraction, was washed with dry pentane to remove
FeCp*2 (40 mg, 0.12 mmol), with dry ether to remove
LiO3SCF3, and recrystallized from EtOH to give
F or m a tion a n d Am in a tion of P er flu or o-2-m eth -
yl-2-p en t en e. (1) Ca t a lyt ic P r oced u r e. FeCp*2
0.10 g, 0.30 mmol) was dissolved in 10 mL of dry thf
together with lithium LiO3SCF3 (1.30 g, 8.33 mmol) and
zinc (5 g). An excess of perfluoro-2-methylpentane (4.0
g, 11.8 mmol) was added, and the mixture was photo-
lyzed for 17 h. FeCp*2 was quantitatively recovered
(
+
-
[FeCp*2 ][CF3SO3 ] (0.088 g, 0.18 mmol). The charac-
terization data were essentially identical to those for
+
-
an authentic sample of [FeCp*2 ][CF3SO3 ]: IR (NaCl
film) 2919 (C-H), 2973 (C-H), 1479 (CH3), 1386 (CH3),
-
1
1
138 (CF3), 1270 cm
(CF3); MS (70 eV) 326; UV
(
0.10 g), and the liquid fraction containing the perfluo-
(EtOH) 208 (9083), 277 (13 800), 314 nm (8900). Two
19
roolefin was separated as explained above.
F NMR
equivalents of FeCp*2 (0.18 mmol) were found by
gravimetry to be consumed per equivalent of 1 (0.09
mmol) formed after reaction with NH3.
spectroscopy of the thf solution showed new resonances
at δ -59.41 (s, br, 3F), -61.9 (m, 3F), -85.1 (s, 3F),
-
118.5 (dd, J ) 17.1, 1F), and -98.8 (m, 2F) identical
(
2) Regen er a tion of F eCp *2 P h otosen sitizer . A
with those of an authentic (Aldrich Chemical Co.)
+
-
suspension of [FeCp*2 ][CF3SO3 ] (0.064, 0.13 mmol)
in dry thf (10 mL) was reduced with granular Zn (0.5 g,
sample of 2. The thf solution of 2 reacted with NH to
3
yield NH F (0.097 g, 2.62 mmol) and 3. Compound 3
4
7
.6 mmol) under nitrogen. After 1 h, the green suspen-
(54 mg, 0.26 mmol, 54% based on reacted fluorocarbon)
sion gave a yellow solution and a white precipitate. The
mixture was dried under vacuum and FeCp*2 (quant
was obtained pure by preparative TLC on silica gel
using a mixture (95:5) CH2Cl2/thf as eluent (Rf ) 0.4,
mp 201-202 °C) Its properties were identical with those
of the authentic material available from a Hg photo-
0
.043 g, 0.13 mmol) was then extracted with pentane
and identified by comparison with authentic material
IR, NMR, anal.).
3) Ca t a lyt ic P r oced u r e. The reaction described
above with CF3C6F11 (6 g, 17.14 mmol), FeCp*2 (2.0 mg,
.1 µmol), and LiO3SCF3 (1.3 g, 8.3 mmol) in thf (30 mL)
was repeated in the presence of granular zinc (0.5 g,
.6 mmol). After a 17-h irradiation, a brown solution
(
5
sensitized reaction.
(
(
2) Deflu or in a tion a n d Am in a tion of P er flu or o-
1
,3-d im eth ylcycloh exa n e. FeCp*2 (0.10 g, 0.30 mmol)
6
was dissolved in 10 mL of dry thf together with LiO3-
SCF3 (1.3 g, 8.3 mmol) and Zn (0.5 g, 7.6 mmol). An
excess of perfluoro-1,3-dimethylcyclohexane (4.0 g, 10.0
mmol) was added, the mixture photolyzed for 17 h, and
a volatile fraction containing 4 was isolated as above;
7
was obtained. The volatile fraction, removed in vacuo
and collected in a liquid N2 trap, gave a solution with
the same characteristics described above. FeCp*2 (0.083
g, 0.27 mmol, 90%) was recovered and compared with
authentic material. A trace of an unidentified soluble
purple material (0.01 g) was also found. The alkene
reacts with NH3 as above to give amine 1 (190 mg, 0.67
mmol, 96%, t.o. 110, conversion 3.9%).
Conditions maximizing conversion are as follows:
CF3C6F11 (4 g, 11.43 mmol), FeCp*2 (100 mg, 0.30
mmol), and LiO3SCF3 (1.3 g, 8.3 mmol) in thf (30 mL),
Zn (0.5 g, 7.6 mmol), and 19 h irradiation. Amine 1 was
isolated as before (390 mg, 1.36 mmol, 96%, conversion
19
it showed F NMR resonances at -195.6, -148.71,
-137.9, -125.0, -113.4, -87.15, -56.9, and -57.0 ppm
together with other signals of smaller intensities. Reac-
tion of this mixture with ammonia at 0 °C gave NH4F
(0.144 g, 3.89 mmol) and 0.52 g of a yellow oil containing
two inseparable isomers with almost identical GC/MS
retention times and identical mass peaks, m/e 336. The
mixture 5 was therefore purified by preparative TLC
on silica gel using CH2Cl2 as eluent to give a yellow solid
(
Rf ) 0.44, 0.32 g, 0.95 mmol, 61% based on reacted
+
+
fluorocarbon): MS (70 eV) 336 (M ), 317 (M - F), 290
(
1
1.9%).
+
+
+
M - F - CNH), 186 (M - C3F6), 166 (M - C3F6 -
Ammonia (20 mL/min, 30 min, 1 atm) was passed
HF); IR (NaCl film) 3570 (N-H), 3448 (N-H), 3350 (N-
H), 3180 (N-H), 1652 (CdC), 1614 (N-H), 1310 (C-
through the solution of 1-perfluoromethyl-1-cyclohexene
obtained as described above to give a precipitate of
NH4F (0.14 g, 10.8 mmol), separated by filtration, and
a yellow solution, evaporated in vacuo to give 1 (0.39 g,
-1
19
F), 1266 (C-F), 1218 (C-F), 1133 cm (C-F); F NMR
CCl2D2) δ -57.0 (CF3, 3F), -57.5 (CF3, 3F), -70.4 (CF3,
(
3
-
g
F), -74.2 (CF3, 3F), -106.1 (d, J FF ) 290 Hz, 1F, CF2),
9
2% based on reacted fluorocarbon). Compound 1 can
g
107.8 (d, J FF ) 290 Hz, 1F, CF2), -115.6 (dCF bon,
be further purified by preparative TLC on silica gel with
CH2Cl2 as eluent (Rf ) 0.6) or by recrystallization from
CCl4. The characterization data were essentially iden-
g
g
J FF ) 297 Hz, 1F, CF2), -115.8 (d, J FF ) 293 Hz, 1F,
g
CF2), -119.8 (d, J FF ) 290 Hz, 1F, CF2), -122.6 (d,
g
g
J FF ) 270 Hz, 1F, CF2), -123.0 (d, J FF ) 290 Hz, 1F,
1
3
tical with the available literature data: MS (70 eV)
g
CF2), -130.7 (d, J FF )290 Hz, 1F, CF2), -184.6 (m, br,
obsd 286 (M ), 267 (M - F), 186 (M+ - C2F4), no
+
+
1
CF, 1F), -184.9 (m, br, CF, 1F); H NMR (CCl2D2) δ
1
literature data; H NMR(CD2Cl2) δ obsd 5.75 (2H), 10.5
5
.7 (br, 2H), 10.6 (br, 1H).
(
-
1H), no literature data; 19F NMR (CD2Cl2) δ -57.8 (3F),
117.9 (2F), -123.0 (2F), -136.6 (2F), lit. (solvent not
Ack n ow led gm en t. We thank the U.S. Department
of Energy for funding and the 3M Corp. for a gift of
fluorochemicals.
(
13) (a) Carter, P. A.; Patrick C. R.; Tatlow, J . C. J . Fluorine Chem.
1
982, 21, 407. (b) Doyle, A. M.; Pedler, A. E. J . Chem. Soc. C 1971,
2
82.
OM970871Q