4284 Organometallics, Vol. 26, No. 17, 2007
Pampaloni et al.
(6.89 g, 33.7 mmol) in DMF (20 mL) was added dropwise to a
well-stirred suspension of NaH (0.815 g, 33.9 mmol) in DMF (10
mL). Diiodomethane (2 mL, 25.1 mmol) was added to the resulting
pale yellow solution, and the reaction mixture was allowed to stir
at 80 °C for 4 days. Diethyl ether (100 mL) was added. The organic
phase was washed with a water solution of K2CO3 (5 × 50 mL).
The solvent was removed under reduced pressure to give a pale
yellow solid. CH2(3,5-(CF3)2Pz)2 was obtained as a colorless
crystalline compound (3.70 g, 52%) by recrystallization from hot
heptane. Anal. Calcd for C11H4F12N4: C, 31.4; H, 1.0; N, 13.3.
Found: C, 31.0; H, 0.9; N, 13.5. IR (ν˜/cm-1, neat): 3169w, 3043w,
1676w, 1574m, 1480w, 1468m,w, 1397m,w, 1383m, 1280m,s,
1271m,s, 1227s, 1219s, 1186s, 1122vs, 1107vs, 1086s, 1042vs,
77%). Mp: 118-125 °C. Anal. Calcd for C18H20CuF9N4O3S: C,
35.6; H, 3.3; N, 9.2. Found: C, 35.0; H, 3.5; N, 9.1. IR (ν˜/cm-1
,
neat): 3130w, 3034w, 2963w, 1492m,w, 1446w, 1423w, 1385m,
1341w, 1319m,w, 1269m,s, 1236vs, 1206s, 1139vs, 1065m,s,
1028s, 1013s, 970m,s, 864m,w, 794s, 784vs, 757m,s, 742m,
1
722m,w. H NMR (C6D6): δ 8.17 (s, 2H, pyr 5-H), 7.01 (s, 2H,
pyr 4-H), 5.86 (s, 2H, CH2), 5.1-4.8 (m, 2H, CHdCH), 2.4-2.0
(m, 4H, CH2CHd), 1.19 (s, 8H). 1H NMR (thf-d8): δ 8.48 (s, 2H,
pyr 5-H), 6.85 (s, 4H, pyr 4-H and CH2), 5.2-5.0 (m, 2H, CHd
CH), 2.23 (s, 4H, CH2CHd), 1.50 (s, 8H). 13C NMR (thf-d8): δ
2
147.5 (q, JC-F ) 39 Hz, CCF3), 138.6 (s, pyr 5-CH), 124.3 (q,
1JC-F ) 270 Hz, CF3), 109.6 (s, pyr 4-CH), 107.7 (s, CHdCH),
68.0 (s, CH2CHd), 33.5 (s, CH2), 30.0 (s, CH2), 29.8 (s, CH2).
1
973s, 843vs, 804m,w, 784m, 737m,w, 719m,s, 696m. H NMR
Synthesis of Cu[CH2(3,5-(CF3)2Pz)2](CO)(OTf). CH2(3,5-
(CF3)2Pz)2 (0.357 g, 0.850 mmol) was dissolved in CH2Cl2 (10 mL).
The solution was saturated with CO at atmospheric pressure, and
Cu(OTf)(toluene)0.5 (0.220 g, 0.851 mmol) was added. A colorless
solid separated out. After 24 h of stirring at room temperature,
pentane (20 mL) was added, and the colorless precipitate was
recovered by filtration, dried quickly under vacuum, and identified
as Cu[CH2(3,5-(CF3)2Pz)2](CO)(OTf) (0.323 g, 58%). Anal. Calcd
for C13H4CuF15N4O4S: C, 23.6; H, 0.6; N, 8.5. Found: C, 23.8;
H, 0.5; N, 8.1. IR (ν˜/cm-1, neat): 3106w, 2127s, 1654w, 1572w,
1488w, 1446w, 1412, 1312m, 1272s, 1213vs, 1194s, 1148vs,
1109m,s, 1056s, 1025vs, 1000m, 986m,w, 975w, 868m,w, 835w,
(CDCl3): δ 6.79 (s, 2H, pyr CH), 6.57 (s, 2H, CH2). 13C NMR
(CDCl3): δ 143.9 (q, 2JC-F ) 41 Hz, CCF3), 134.7 (q, 2JC-F ) 41
Hz, CCF3), 119.9 (q, 1JC-F ) 269 Hz, CF3), 118.8 (q, 1JC-F ) 270
Hz, CF3), 107.8 (s, pyr CH), 63.7 (s, CH2). EI-MS: 217 m/z [M+
- 3,5-(CF3)2Pz, 100], 147 m/z [M+ - 3,5-(CF3)2Pz - HCF3, 9],
69 m/z [14].
Synthesis of r,r′-Bis[3,5-bis(trifluoromethyl)-1-pyrazolyl]-
toluene, PhCH(3,5-(CF3)2Pz)2. A solution of 3,5-bis(trifluorom-
ethyl)pyrazole (8.82 g, 43.2 mmol) in DMF (10 mL) was added
dropwise to a well-stirred suspension of NaH (1.03 g, 42.9 mmol)
in DMF (15 mL). R,R′-Dibromotoluene (5.44 g, 21.7 mmol) was
added to the resulting pale yellow solution, and the reaction mixture
was allowed to stir at 80 °C for 3 days and at 100 °C for the
following 36 h. Diethyl ether (100 mL) was added. The organic
phase was washed with a water solution of K2CO3 (5 × 50 mL).
The solvent was removed under reduced pressure to give a brown-
yellow solid. PhCH(3,5-(CF3)2Pz)2 was obtained as a pale yellow
crystalline compound (4.29 g, 40%) by sublimation of the crude
product (70 °C, 10-2 Torr). Anal. Calcd for C17H8F12N4: C, 41.1;
1
797w, 749m,w, 736w, 725w, 697w. H NMR (C6D6): δ 6.60 (s,
1
2H, pyr CH), 5.34 (s, 2H, NCH2N). H NMR (thf-d8): δ 7.33 (s,
2H, pyr CH), 6.79 (s, 2H, NCH2N). 13C NMR (thf-d8): δ 143.7
(q, 2JC-F ) 39 Hz, CCF3), 134.9 (q, 2JC-F ) 41 Hz, CCF3), 120.8
1
1
(q, JC-F ) 269 Hz, CF3), 119.6 (q, JC-F ) 270 Hz, CF3), 108.3
(s, pyr CH), 64.6 (s, NCH2N).
Synthesis of Cu[CH2(3,5-(CF3)2Pz)2](coe)(OTf). Cu(OTf)-
(toluene)0.5 (0.804 g, 3.12 mmol) was added to a mixture of
CH2(3,5-(CF3)2Pz)2 (1.31 g, 3.12 mmol) and coe (0.462 g, 4.20
mmol) in toluene (25 mL). After 24 h of stirring at room
temperature, heptane was added (30 mL), and the resulting colorless
suspension was filtered. The solid was recovered, dried in vacuo,
and identified as Cu[CH2(3,5-(CF3)2Pz)2](coe)(OTf) (1.10 g, 48%).
Anal. Calcd for C20H18CuF15N4O3S: C, 32.3; H, 2.4; N, 7.5.
H, 1.6; N, 11.3. Found: C, 41.0; H, 1.5; N, 10.9. IR (ν˜/cm-1
,
neat): 3153w, 1742w, 1624w, 1573m,w, 1494m, 1456w, 1390w,
1275m,s, 1245m, 1216s, 1096s, 1041vs, 975s, 862m, 838m,s,
1
754m,s, 730s, 690s. H NMR (CDCl3): δ 7.85 (s, 1H, PhCH),
7.52-7.22 (m, 5H, Ph), 7.04 (s, 2H, pyr CH). 13C NMR (CDCl3):
δ 143.0 (q, 2JC-F ) 42 Hz, CCF3), 133.7 (q, 2JC-F ) 41 Hz, CCF3),
131.7 (s, 1-CPh), 130.5 (s, CHPh), 128.8 (s, CHPh), 128.1 (s, CHPh),
Found: C, 32.0; H, 2.5; N, 7.9. Mp: 126-131 °C. IR (ν˜/cm-1
,
1
1
119.9 (q, JC-F ) 269 Hz, CF3), 118.8 (q, JC-F ) 270 Hz, CF3),
107.0 (s, pyr CH), 75.7 (s, PhCH). EI-MS: 496 m/z [M+, 2], 427
m/z [M+ - CF3, 8], 293 m/z [M+ - 3,5-(CF3)2Pz, 100], 223 m/z
[M+ - 3,5-(CF3)2Pz - CF3, 2].
neat): 3100w, 2938m,w, 2856w, 1573w, 1483w, 1464w, 1411w,
1399w, 1317m, 1267m,s, 1243m, 1219m,s, 1178vs, 1158vs, 1143vs,
1100m,s, 1050m,s, 1031m,s, 1012s, 991m,s, 898w, 874m,w, 841m,
1
796m, 749m, 734w, 723w, 693w, 629s, 582m, 566m. H NMR
Synthesis of Cu[CH2(3-CF3Pz)2](CO)(OTf). Cu(OTf)(tolu-
ene)0.5 (0.280 g, 1.08 mmol) was dissolved in toluene (20 mL); the
solution was saturated with CO, and a colorless solid formed. After
addition of CH2(3-CF3Pz)2 (0.291 g, 1.02 mmol), the suspension
was stirred for 24 h at room temperature. The solid was recovered
by filtration, dried in vacuo for a short time, and identified as Cu-
[CH2(3-CF3Pz)2](CO)(OTf) (0.392 g, 74%). Crystals suitable for
X-ray diffraction were grown from THF/toluene. Anal. Calcd for
C11H6CuF9N4O4S: C, 25.2; H, 1.2; N, 10.7. Found: C, 25.0; H,
1.5; N, 10.9. IR (ν˜/cm-1, neat): 3157w, 3135w, 3048w, 2120s,
1496m,w, 1426w, 1383m, 1339w, 1321m, 1290m,s, 1235vs, 1221s,
1207s, 1188s, 1139vs, 1075m,s, 1066s, 1021vs, 973s, 891w, 788s,
756m,s, 743m, 723m,w. 1H NMR (thf-d8): δ 8.45 (s, 2H, pyr 5H),
(CDCl3): δ 7.03 (s, 2H, pyr CH), 6.69 (s, 2H, NCH2N), 5.23 (m,
2H, CHdCH), 2.4-2.0 (m, 4H, CH2CHd), 1.47 (s, 8H). 13C NMR
2
2
(thf-d8): δ 143.8 (q, JC-F ) 39 Hz, CCF3), 134.8 (q, JC-F ) 41
Hz, CCF3), 119.7 (q, 1JC-F ) 269 Hz, CF3), 117.9 (q, 1JC-F ) 270
Hz, CF3), 108.3 (s, pyr CH), 106.3 (s, CHdCH), 64.6 (s, NCH2N),
29.7 (s, CH2CHd), 26.0 (s, CH2), 25.9 (s, CH2).
Synthesis of Cu[PhCH(3,5-(CF3)2Pz)2](CO)(OTf). PhCH(3,5-
(CF3)2Pz)2 (0.262 g, 0.521 mmol) was dissolved in toluene (10 mL).
The solution was saturated with CO at atmospheric pressure, and
Cu(OTf)(toluene)0.5 (0.132 g, 0.53 mmol) was added. After 24 h
of stirring at room temperature, heptane (20 mL) was added, and
a colorless precipitate formed. After filtration, the solid was dried
quickly under vacuum and identified as Cu[PhCH(3,5-(CF3)2Pz)2]-
(CO)(OTf) (0.172 g, 45%). Anal. Calcd for C19H8CuF15N4O4S: C,
3
6.92 (d, 2H, J ) 1.8 Hz), 6.79 (s, 2H, NCH2N). 13C NMR (thf-
d8): δ 144.8 (q, 2JC-F ) 38 Hz, CCF3), 136.2 (s, pyr 5CH), 121.1
1
31.0; H, 1.1; N, 7.6. Found: C, 30.8; H, 1.5; N, 7.9. IR (ν˜/cm-1
,
(q, JC-F ) 269 Hz, CF3), 106.8 (s, pyr 4CH), 64.3 (s, NCH2N).
neat): 3066w, 2117s, 2108s, 1644w, 1610m, 1575m,w, 1496w,
1449m,w, 1286s, 1259s, 1214vs, 1167vs, 1079m,w, 1016vs, 980m,
926m,w, 896w, 875m,w, 752s, 734m, 692s. 1H NMR (CDCl3): δ
8.04 (s, 1H, PhCH), 7.7-7.1 (m, 5H, Ph), 6.34 (s, 1H, pyr CH),
6.31 (s, 1H, pyr CH). 13C NMR (CDCl3): δ 168.3 (s, CO), 166.3
(s, CO), 146.1 (q, 2JC-F ) 41 Hz, CCF3), 137.8 (q, 2JC-F ) 41 Hz,
CCF3), 133.8 (s, 1-CPh) 131.5(s, CHPh), 130.1 (s, CHPh), 124.8 (s,
Synthesis of Cu[CH2(3-CF3Pz)2](coe)(OTf). Cu(OTf)(tolu-
ene)0.5 (0.830 g, 3.20 mmol) was added to a mixture of CH2(3-
CF3Pz)2 (0.911 g, 3.20 mmol) and coe (0.39 g, 3.50 mmol) in
toluene (15 mL). A colorless solid separated out. After 24 h of
stirring at room temperature, heptane was added (30 mL), and the
colorless suspension was filtered. The solid was recovered, dried
in vacuo, and identified as Cu[CH2(3-CF3Pz)2](coe)(OTf) (1.52 g,