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J Chem Crystallogr (2011) 41:654–663
tert-butoxide (0.75 g, 7.8 mmol), and allyl[1,3-bis(2,6-
diisopropylphenyl)-imidazol-2-ylidene]palladium(II)chlo-
ride (91 mg, 0.16 mmol) were placed in a Schlenk flask in
a drybox. The flask was removed, and toluene (100 mL)
was added via cannula. The reaction was stirred under an
argon atmosphere at 80 °C for 5 days. After cooling to
room temperature, CH2Cl2 (100 mL) was added, and the
mixture was extracted twice with brine solution. The sol-
vent was removed from the organic phase under reduced
pressure, and the resulting residue was purified by column
chromatography on silica gel (eluent: 2.5% ethyl acetate in
CH2Cl2 (ca. 15 mL) The solvent was removed under vac-
uum, and the solid was dissolved in methanol, followed by
filtration through a medium porosity sintered-glass frit.
Slow evaporation of the filtrate yielded 0.186 g (36%)
colorless crystals. Mp (TGA; decomp.): 220–222 °C. FTIR
(neat, ATR, cm-1): 3058 (w, aromatic mC–H), 2969 (s, alkyl
m
C–H), 2931 (w, alkyl mC–H), 2912 (w, alkyl mC–H), 2877 (m,
alkyl mC–H), 2649 (w, vbr), 1637 (w), 1598–1433 (s, aro-
matic dC=C), 1366 (m), 1331 (s, 3o aromatic mC–N), 1299
(w), 1229 (m), 1157 (m), 1045 (s, mB–F), 823 (s), 759 (s). 1H
NMR (CD3OD): d 8.58 [2H, d, J(H–H) = 9.3 Hz, CH,
4-quin], 8.39 [2H, dd, J(H–H) = 8.3 Hz, J(H–H) =
0.8 Hz, CH, 6-quin], 8.08 [2H, dd, J(H–H) = 8.0 Hz, J(H–
H) = 1.3 Hz, CH, 9-quin], 8.08 [2H, ddd, J(H–H) =
8.3 Hz, J(H–H) = 7.1 Hz, J(H–H) = 1.3 Hz, CH, 7-quin],
7.80 [1H, t, J(H–H) = 8.2 Hz, p–CH, Ph], 7.78 [2H,
ddd, J(H–H) = 8.0 Hz, J(H–H) = 7.1 Hz, J(H–H) =
0.8 Hz, CH, 8-quin], 7.66 [2H, d, J(H–H) = 8.2 Hz,
m-CH, Ph], 6.87 [2H, d, J(H–H) = 9.3 Hz, CH, 3-quin],
2.90 [2H, sept, J(H–H) = 6.8 Hz, CH(CH3)2], 1.09 [12 H,
d, J(H–H) = 6.8 Hz, CH(CH3)2]. 13C NMR (CD3OD):
d 155.23, 148.72, 144.45, 141.43, 134.57, 133.55, 133.42,
129.78, 128.99, 128.12, 126.35, 125.03, 115.06, 29.85,
24.41.
hexanes). Recrystallization from
a very slow (ca.
8 months) evaporation of a 1:1 mixture of Et2O and EtOH
gave translucent yellow plates suitable for diffraction.
Yield: 0.75 g (39%), 97% pure by GC–MS. Mp (TGA;
sublim.): 210–212 °C. MS (EI, %): m/z 381.2 (M?, 1.0),
338.2 (M?–iPr, 100). FTIR (neat, ATR, cm-1): 3064 (w,
aromatic mC–H), 3016 (w, aromatic mC–H), 2957 (w, alkyl
m
C–H), 2926 (m, alkyl mC–H), 2906 (w, alkyl mC–H), 2866 (w,
alkyl mC–H), 1617 (m), 1602 (m), 1584 (s), 1570–1423 (s,
aromatic dC=C), 1384 (m), 1335 (s, 3o aromatic mC–N), 1310
(s), 1287 (s), 1260(s), 1150 (m), 1054 (m), 826 (m), 821
1
(s), 757 (s). H NMR (CD3OD): d 8.21 [1H, ddd, J(H–
H) = 5.0 Hz, J(H–H) = 2.0, Hz, J(H–H) = 0.8 Hz, CH,
6-py], 8.06 [1H, d, J(H–H) = 9.0 Hz, CH, 4-quin], 7.74
[1H, ddd, J(H–H) = 8.1 Hz, J(H–H) = 1.5 Hz, J(H–
H) = 0.6 Hz, CH, 9-quin], 7.69 [1H, ddd, J(H–
H) = 8.5 Hz, J(H–H) = 1.2 Hz, J(H–H) = 0.6 Hz, CH,
6-quin], 7.67 [1H, ddd, J(H–H) = 8.5 Hz, J(H–H) = 7.3,
J(H–H) = 2.0 Hz, CH, 4-py], 7.58 [1H, ddd, J(H–
H) = 8.5 Hz, J(H–H) = 6.9, Hz, J(H–H) = 1.5 Hz, CH,
7-quin], 7.45 [1H, t, J(H–H) = 7.8 Hz, p–CH, Ph], 7.38
[1H, ddd, J(H–H) = 8.1 Hz, J(H–H) = 6.9, Hz, J(H–
H) = 1.2 Hz, CH, 8-quin], 7.32 [2H, d, J(H–H) = 7.8 Hz,
m-CH, Ph], 7.11 [1H, ddd, J(H–H) = 8.5 Hz, J(H–
H) = 0.9, Hz, J(H–H) = 0.8 Hz, CH, 3-py], 7.04 [1H, d,
J(H–H) = 9.0 Hz, CH, 3-quin], 7.00 [1H, ddd, J(H–
H) = 7.3 Hz, J(H–H) = 5.0, Hz, J(H–H) = 0.9 Hz, CH,
5-py], 3.15 [2H, sept, J(H–H) = 6.9 Hz, CH(CH3)2], 0.96
[6 H, d, J(H–H) = 6.9 Hz, CH(CH3)2], 0.94 [6 H, d, J(H–
H) = 6.9 Hz, CH(CH3)2]. 13C NMR (CD3OD): d 158.80,
157.65, 149.44, 148.75, 148.50, 139.52, 139.28, 138.82,
130.94, 130.38, 128.69, 128.21, 126.66, 126.14, 125.75,
119.33, 117.51, 117.15, 29.89, 24.31, 24.19.
(N-Mesityl-N-(2-pyridyl)-N-(2-
quinolyl)amine)hydrogen Tetrafluoroborate (4)
This compound was prepared in an analogous manner to
that of 3, using MesN(py)quin (0.339 g, 1.0 mmol) as
ligand. Yield: 0.191 g (45%) colorless crystals. Mp (TGA;
decomp.): 197–199 °C. FTIR (neat, ATR, cm-1): 3120 (m,
aromatic mC–H), 3061 (w, aromatic mC–H), 2983 (w, alkyl
m
(w), 2645 (w, vbr), 1624 (s), 1597 (s), 1506–1437 (s,
C–H), 2926 (m, alkyl mC–H), 2858 (w, alkyl mC–H), 2736
aromatic dC=C), 1364 (3o aromatic mC–N), 1321 (m), 1267
1
(m), 1149 (m), 1031 (s, mB–F), 831 (s), 762 (s). H NMR
(CD3OD): d 8.81 [1H, ddd, J(H–H) = 5.4 Hz, J(H–
H) = 1.9 Hz, J(H–H) = 0.9 Hz, CH, 6-py], 8.57 [1H, dd,
J(H–H) = 9.4 Hz, J(H–H) = 0.7 Hz, CH, 4-quin], 8.32
[1H, ddd, J(H–H) = 8.5 Hz, J(H–H) = 1.5 Hz, J(H–H) =
0.8 Hz, CH, 9-quin], 8.07 [1H, ddd, J(H–H) = 8.4 Hz,
J(H–H) = 7.3 Hz, J(H–H) = 1.9 Hz, CH, 4-py], 8.05 [1H,
dd, J(H–H) = 8.5 Hz, J(H–H) = 1.0 Hz, CH, 6-quin],
8.01 [1H, ddd, J(H–H) = 8.5 Hz, J(H–H) = 7.2 Hz, J(H–
H) = 1.3 Hz, CH, 7-quin], 7.74 [1H, ddd, J(H–H) =
8.1 Hz, J(H–H) = 7.0 Hz, J(H–H) = 1.0 Hz, CH, 8-quin],
7.51 [1H, ddd, J(H–H) = 7.3 Hz, J(H–H) = 5.4 Hz, J(H–
H) = 1.0 Hz, CH, 5-py], 7.32 (2H, s, m-C6H2), 6.75 [1H,
d, J(H–H) = 9.4 Hz, CH, 3-quin], 6.71 [1H, ddd, J(H–
H) = 8.4 Hz, J(H–H) = 1.0 Hz, J(H–H) = 0.9 Hz, CH,
3-py], 2.47 (3H, s, p-CH3), 2.07 (6H, s, o-CH3). 13C NMR
(CD3OD): d 155.27, 153.96, 146.01, 144.97, 144.17,
(N-(2,6-Diisopropyl)phenyl-N,N-(2,20-
diquinolyl)amine)hydrogen Tetrafluoroborate (3)
In a 25 mL round bottom flask, (2,6-iPr2C6H3)N(quin)2
(0.431 g, 1.0 mmol) was dissolved in MeOH (15 mL).
With stirring, KBF4 (0.130 g, 1.0 mmol) dissolved in
dilute HCl (5 mL) was slowly added. The mixture was
allowed to stir for 30 min, followed by extraction with
123