8372 Inorganic Chemistry, Vol. 48, No. 17, 2009
Ditri et al.
The reaction mixture was allowed to stir for 36 h after which,
50 mL of H2O was added. The organic and aqueous layers
were then separated, and the latter was washed with Et2O (3 Â
200 mL). The combined Et2O extracts were stirred over MgSO4,
filtered, and dried in vacuo. The resulting residue was then
slurried in cold hexanes (100 mL, 0 ꢀC), filtered, and dried in
vacuo to afford HC(O)NHArDipp2 as a colorless solid. Yield:
7.50 g, 16.70 mmol, 87.3%. 1H NMR (400.1 MHz, CDCl3,
20 ꢀC): δ=7.64 (d, 1H, J=11 Hz, HC(O)), 7.40 (t, 2H, J=8 Hz,
p-Dipp), 7.29 (t, 2H, J=7 Hz, p-Ph), 7.50 (d, 4H, J=8 Hz, m-
dipp), 7.19 (d, 2H, J=8 Hz, m-Ph), 6.59 (d, 1H, J=11 Hz, H-N),
2.62 (sept, 4H, J=7 Hz, CH(CH3)2) 1.12 (d, 24H, J=7 Hz,
CH(CH3)2) ppm. 13C{1H} NMR (100.6 MHz, CDCl3, 20 ꢀC):
δ=162.6 (HC(O)N), 146.7, 134.9, 133.4, 131.8, 130.8, 129.4,
124.6, 123.9, 30.9 (CH(CH3)2), 25.0 (CH(CH3)2), 23.3 (CH-
Synthesis of (OTf)Cu(CNArDipp2)2. To a CH2Cl2 solution of
(C6H6)[CuOTf]2 (0.050 g, 0.099 mmol, 3 mL) was added a
CH2Cl2 solution of CNArDipp2 (0.170 g, 0.401 mmol, 4.04 equiv,
5 mL). The reaction mixture was allowed to stir for 3 h, after
which all volatile materials were removed under reduced pres-
sure. Dissolution of the resulting colorless residue in CH2Cl2
(3 mL) followed by filtration and storage at -35 ꢀC for 12 h
resulted in colorless crystals, which were collected and dried in
vacuo. Yield: 0.124 g, 0.117 mmol, 59%. 1H NMR (400.1 MHz,
C6D6, 20 ꢀC): δ=7.34 (t, 4H, J=8 Hz, p-Dipp), 7.19 (d, 8H, J=8
Hz, m-Dipp), 6.86 (s, 6H, p-Ph + m-Ph), 2.50 (setp, 8H, J=6 Hz,
CH(CH3)2), 1.21 (d, 24H, J=6 Hz, CH(CH3)2), 1.06 (d, 24H, J=
6 Hz, CH(CH3)2) ppm. 13C{1H} NMR (100.6 MHz, C6D6,
20 ꢀC): δ = 166.5 (CtN), 146.3, 140.3, 133.5, 133.3, 130.2,
130.0, 129.9, 123.7, 31.5 (CH(CH3)2), 24.6 (CH(CH3)2), 24.2
(CH(CH3)2) ppm. 19F{1H}NMR (282.3 MHz, C6D6, 20 ꢀC):
δ = -78.0 ppm. FTIR (KBr pellet): (νCN) 2167 cm-1 also
3063, 2962, 2928, 2869, 1596, 1579, 1460, 1412, 1385, 1364,
1316, 1235, 1209, 1165, 1056, 1020, 806, 757, 636 cm-1. FTIR
(C6D6, NaCl windows): (νCN) 2165 cm-1. (13C{1H} NMR and
(CH3)2) ppm. FTIR (KBr pellet): (νNH) 3448 cm-1, (νCO
)
1699 cm-1 also 3057, 2959, 2882, 2862, 1462, 1424, 1383, 1361,
1324, 1299, 1057, 800, 791, 763, 747 cm-1. Anal. Calcd For C31H39-
NO: C, 84.30; H, 8.91; N, 3.17. Found: C, 83.40; H, 8.88; N, 3.08.
Synthesis of CNArDipp2. To a CHCl3 solution of HC-
(O)NHArDipp2 (21.23 g, 48.11 mmol, 1 equiv, 150 mL) was
added diisopropylamine (34.31 g, 336.8 mmol, 7 equiv). The
solution was cooled to 0 ꢀC under an N2 atmosphere and POCl3
(11 mL, 18.44 g, 120.3 mmol, 2.5 equiv) was added dropwise via
syringe. The resulting mixture was allowed to stir for 48 h, after
which 150 mL of an aqueous 1.5 M Na2CO3 was transferred via
cannula. After an additional 2 h of stirring, the organic and
aqueous layers were separated, and the latter was washed with
CH2Cl2 (3 Â 200 mL). The combined organic extracts were
stirred over MgSO4, filtered, and dried in vacuo. The resulting
residue was slurried in cold acetonitrile (100 mL, 0 ꢀC), filtered
and dried in vacuo to afford isocyanide CNArDipp2 as a colorless
solid. Yield: 18.25 g, 430.7 mmol, 90%. 1H NMR (400.1 MHz,
CDCl3, 20 ꢀC): δ=7.51 (t, 1H, J=8 Hz, p-Ph), 7.41 (t, 2H, J=
8 Hz, p-Dipp), 7.28 (d, 2H, J=8 Hz, m-Ph), 6.26 (d, 4H, J=8 Hz,
m-Dipp), 2.54 (sept, 4H, J=7 Hz, CH(CH3)2), 1.18 (d, 12H, J=
7 Hz, CH(CH3)2), 1.14 (d, 12H, J = 7 Hz, CH(CH3)2) ppm.
13C{1H} NMR (100.6 MHz, C6D6, 20 ꢀC): δ=171.9 (CtN),
146.7, 139.4, 135.0, 129.7, 129.6, 128.6, 123.4, 31.5 (CH(CH3)2),
24.5 (CH(CH3)2), 24.2 (CH(CH3)2) ppm. FTIR (KBr pellet):
(νCN) 2124 cm-1 also 3061, 3025, 2959, 2925, 2867, 1578, 1458,
1417, 1382, 1363, 1328, 1252, 1177, 1055, 1039, 824, 806, 792,
758 cm-1. FTIR (C6D6, NaCl windows): (νCN) 2118 cm-1 also
3062, 3023, 2962, 2929, 2868, 2118, 1616, 1594, 1580, 1460, 1419,
1385, 1363, 1324, 1180, 1052, 811, 794, 760 cm-1. Anal. Calcd
For C31H37N: C, 87.89; H, 8.80; N, 3.31. Found: C, 88.03; H,
8.61; N, 3.12.
FTIR signatures for (OTf)Cu(CNArDipp2
)
and [(THF)2-
2
Cu(CNArDipp2)2]OTf in C6D6 solution are nearly identical, see
above. We attribute this to both THF dissociation in solution
and desolvation under prolonged vacuum). Anal. Calcd for
C63H74F3N2O3SCu: C, 71.39; H, 7.04; N, 2.64. Found: C,
71.23; H, 7.12; N, 2.59.
Synthesis of [(Et2O)Ag(CNArMes2)3]OTf. To a THF solution
of AgOTf (0.050 g, 0.196 mmol, 3 mL) was added a THF
solution of CNArMes2 (0.200 g, 0.589 mmol, 3 equiv, 5 mL).
The reaction mixture was allowed to stir for 3 h, after which all
volatile materials were removed under reduced pressure. Dis-
solution of the resulting colorless residue in a 15:1 Et2O/THF
mixture (4 mL total) followed by filtration and storage at
-35 ꢀC for 24 h resulted in colorless crystals, which were
collected and dried in vacuo. Yield: 0.162 g, 0.120 mmol, 61%.
1H NMR (400.1 MHz, C6D6, 20 ꢀC): δ=6.93 (t, 3H, J=8 Hz,
p-Ph), 6.89 (s, 12H, m-Mes), 6.75(d, 6H, J=8 Hz, m-Ph), 3.27
(q, 4H, J=7 Hz, H3CCH2O), 2.20 (s, 18H, p-CH3), 2.01 (s, 36H,
o-CH3), 1.12 (t, 6H, J=7 Hz, H3CCH2O) ppm. 13C{1H} NMR
(100.6 MHz, C6D6, 20 ꢀC): δ=140.8, 138.6, 136.0, 134.1, 130.7,
129.9, 129.4, 21.5 (p-CH3-Mes), 20.5 (o-CH3-Mes) ppm (the
CtN resonance was not conclusively identified after prolonged
scanning). 19F{1H} NMR (282.3 MHz, C6D6, 20 ꢀC): δ =
-77.9 ppm. FTIR (KBr pellet): (νCN) 2166 cm-1, also 2977,
2947, 2919, 2858, 2613, 1577, 1457, 1379, 1279 cm-1. Anal.
Calcd for C80H85F3N3O4SAg: C, 71.20; H, 6.35; N, 3.11. Found:
C, 71.29; H, 6.12; N, 3.19.
Synthesis of (K2-OTf)Ag(CNArDipp2)2. To a THF solution of
AgOTf (0.030 g, 0.118 mmol, 5 mL) was added a THF solution
of CNArDipp2 (0.100 g, 0.236 mmol, 5 mL). The reaction mixture
was allowed to stir for 3 h, after which all volatile materials were
removed under reduced pressure. Dissolution of the resulting
colorless residue in an Et2O/n-hexane mixture (1:1, 2 mL total)
followed by filtration and storage at -35 ꢀC for 12 h resulted in
colorless crystals, which were collected and dried in vacuo.
Yield: 0.070 g, 0.063 mmol, 54%. 1H NMR (400.1 MHz, CDCl3,
20 ꢀC): δ=7.33 (t, 4H, J=8 Hz, p-Dipp), 7.18 (d, 8H, J=8 Hz, m-
Dipp), 6.9 (t, 1H, J=9 Hz, m-Ph), 6.8 (t, 1H, J=9 Hz, m-Ph),
6.80 (d, 4H, J=7 Hz, p-Ph), 2.43 (sept, 8H, J=7 Hz, CH(CH3)2),
1.20 (d, 24H, J = 7 Hz, CH(CH3)2), 1.03 (d, 24H, J = 7 Hz,
CH(CH3)2) ppm. 13C{1H} NMR (100.6 MHz, CDCl3, 20 ꢀC):
δ=169.6 (CtN), 146.5, 140.4, 133.4, 130.6, 130.3, 130.0, 127.3,
127.1, 123.8, 67.9 (CF3), 31.5 (CH(CH3)2), 24.5 (CH(CH3)2),
24.2 (CH(CH3)2) ppm. 19F{1H} NMR (282.3 MHz, C6D6,
Synthesis of [(THF)2Cu(CNArDipp2)2]OTf. To a THF solu-
tion of (C6H6)[CuOTf]2 (0.074 g, 0.147 mmol, 3 mL) was added
a THF solution of CNArDipp2 (0.250 g, 0.590 mmol, 4 equiv,
10 mL). The reaction mixture was allowed to stir for 3 h, after
which time all volatile materials were removed under reduced
pressure. Dissolution of the resulting colorless residue in THF
(5 mL) followed by filtration and storage at -35 ꢀC for 36 h
resulted in colorless crystals, which were collected and dried in
vacuo. Yield: 0.110 g, 0.091 mmol, 62%. 1H NMR (400.1 MHz,
C6D6, 20 ꢀC): δ=7.34 (t, 4H, J=8 Hz, p-Dipp), 7.18 (d, 8H, J=
8 Hz, m-Dipp), 6.86 (s, 6H, p-Ph + m-Ph), 3.48 (bs, 8H, THF),
2.51 (setp, 8H, J=7 Hz, CH(CH3)2), 1.40 (bs, 8H, THF), 1.22 (d,
24H, J=7 Hz, CH(CH3)2), 1.06 (d, 24H, J=7 Hz, CH(CH3)2)
ppm.13C{1H} NMR (100.6 MHz, C6D6, 20 ꢀC): δ = 166.5
(CtN), 146.3, 140.3, 133.5, 133.3, 130.2, 130.0, 129.9, 123.7,
31.5 (CH(CH3)2), 24.6 (CH(CH3)2), 24.2 (CH(CH3)2) ppm.
19F{1H} NMR (282.3 MHz, C6D6, 20 ꢀC) δ=-78.3 ppm. FTIR
(KBr pellet): (νCN) 2167 cm-1 also 3063, 2964, 2928, 2569, 1578,
1460, 1363, 1315, 1236, 1210, 1027, 757, 636 cm-1. FTIR (C6D6,
20 ꢀC) δ = -77.7 ppm. FTIR (C6D6, NaCl windows): (νCN
)
2176 cm-1 also 3231, 3061, 2962, 2926, 2862, 2390, 2376, 2362,
2174, 1616, 1460, 1333, 1299, 1235, 1221, 1158, 1027, 755, 639
cm-1. Anal. Calcd for C63H74AgF3N2O3S: C, 68.53; H, 6.76; N,
2.54. Found: C, 70.91; H, 7.26; N, 2.31.
NaCl windows): (νCN
C71H90F3N2O5SCu: C, 70.82; H, 7.53; N, 2.33. Found: C,
)
2165 cm-1
.
Anal. Calcd for
71.32; H, 7.34; N, 2.27.