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ppm. 13C{ H} NMR (100.55 MHz, CD
54.92 (C=N), 150.71 (Car.), 149.89 (Car.), 136.83 (Car.), 132.01 (3.98ϫ10 ), 554 (1.10ϫ10 ) nm. Crystal data for C40
ar.), 128.39 (CHar.), 125.70 (CHar.), 123.34 (Car.), 119.23 (CHar.), = 1286.86, 0.10ϫ0.08ϫ0.06 mm, orthorhombic, space group
15.59 (CHar.), 115.48 (CHar.), 40.04 (CH ) ppm. IR (KBr disc): ν˜ Pbam, a = 14.715(14), b = 15.401(14), c = 12.396(10) Å, β = 90.00°,
2999 (w), 2922 (m), 2870 (m), 2798 (w), 1627 (vs), 1571 (s), 1493 V = 2809(4) Å , Z = 2, dcalcd. = 1.521 Mgm , Mo-K
m), 1456 (w), 1424 (w), 1396 (w), 1364 (s), 1264 (w), 1231 (m), (graphite-monochromated, λ = 0.71073 Å), T = 100 K, θrange
1
Cl
): δ = 155.09 (C=N),
(7.08ϫ10 ), 288 (4.72ϫ10 ), 374 (1.69ϫ10 ), 462 (3.26ϫ10 ), 487
4
4
4
4
2
2
4
4
1
58 24 12 4
H F N P :
(C
M
r
1
=
(
3
3
–3
α
radiation
=
1
7
136 (s), 1098 (w), 1061 (w), 1003 (w), 986 (m), 923 (w), 835 (w),
1.91–25.02°. Reflections measd. 52111, indep. 2614, Rint = 0.1035.
Final R indices [IϾ2σ(I)]: R = 0.0752, wR = 0.1794.
–1
–5
–1
68 (w), 750 cm . UV/Vis (CH
3
CN, c = 1.03ϫ10 molL ): λ (ε,
1
2
–1
–1
4
4
4
Lmol cm ) = 220 (8.37ϫ10 ), 237 (8.39ϫ10 ), 360 (3.87ϫ10 ),
4
H] 354.25265; found 354.25272; calcd. for C40H N
7
3
[(4b)H ](PF : To a solution of 3b (47 mg, 0.067 mmol) dissolved
2
6 4
)
30 6
69 (3.4ϫ10 ) nm. HRMS (ESI+): calcd. for C20H N [M + 2
2+
[M + H]+
in dry CH Cl (20 mL) was added AgPF (70.0 mg, 0.276 mmol).
2
2
6
59 6
After stirring at room temperature in the dark for 24 h, the reaction
mixture was filtered. The product was washed twice with dry
07.49802; found 707.49895.
4
,4Ј,5,5Ј-Tetrakis(dimethylethyleneguanidinyl)binaphthyl (3b): To a
2 2 50 24 12 4
CH Cl (10 mL) and dried under vacuum (87%). C40H F N P
solution of 1,3-dimethyl-2-imidazolidinone (1.0 mL, 9.3 mmol) dis-
solved in dry CHCl (20 mL) was added oxalyl chloride (3.9 mL,
4.7 mmol) dropwise. The yellow solution was stirred at reflux for
0 h. The solvent was removed under vacuum. The remaining solid,
-chloro-1,3-dimethylethyleneformamidinium chloride (9.3 mmol),
(
1278.28): calcd. C 37.57, H 3.94, N 13.14; found C 37.05, H 4.00,
1
3
3
N 12.71. H NMR (600.13 MHz, CD CN): δ = 12.65 (s, 2 H, NH),
4
2
2
3
3
9
.18 (d, J = 9.6 Hz, 4 H, Har.), 7.52 (d, J = 9.6 Hz, 4 H, Har.),
.09 (s, 8 H, CH ) 3.97 (s, 8 H, CH ), 2.99 [s, 24 H, N(CH
CN): δ = 159.85 (C=N), 156.89,
35.64, 128.06, 125.98, 123.38, 111.10, 49.63 (CH ), 34.11 (CH
ppm. MS (ESI+): m/z (%) = 232.7 (71.9) [M – 4 PF
4
2
2
3 2
) ]
ppm. 13C NMR (150.90 MHz, CD
3
was washed twice with Et
(
(
2
O (8 mL), dissolved in dry CH
10 mL) and then added dropwise to a dry CH Cl solution
25 mL) containing 4,4Ј,5,5Ј-tetraaminobinaphthyl (0.51 g,
.64 mmol) and triethylamine (2.7 mL, 19.68 mmol) at –10 °C. The
2 2
Cl
1
2
3
)
3+
2
2
– H] , 348.4
– 2H] . IR (CsI disc): ν˜ = 2968 (w), 2929 (w),
596 (s), 1553 (m), 1416 (w), 1356 (w), 1302 (m), 1211 (m), 1031
6
2+
(
1
(
=
100) [M – 4 PF
6
1
reaction mixture was stirred for an additional period of 3 h and
warmed up slowly to room temperature during this time. The solu-
tion was extracted with HCl (5%) and then deprotonated with
–1
3
w), 1012 (w), 974 (w), 835 (vs), 559 (s) cm . UV/Vis (CH CN, c
8.74ϫ10 molL ): λ (ε, Lmol cm ) = 216 (7.09ϫ10 ), 287
4.98ϫ10 ), 375 (1.29ϫ10 ), 460 (3.85ϫ10 ), 486 (5.09ϫ10 ), 599
–6
–1
–1
–1
4
4
4
4
4
(
(
KOH solution (50%). After extracting with CH
2
Cl
2
, the combined
4
1.20ϫ10 ) nm.
organic phases were dried with K CO , and the solvent was re-
2
3
[
(4a)H
in dry CH
88.8 mg, 0.35 mmol, 5 equiv.) dissolved in dry CH
2
](I
3
)
3
I: To a solution of 3a (50.0 mg, 0.07 mmol) dissolved
CN (10 mL) was added dropwise a solution of iodine
CN (10 mL).
moved under vacuum. The brown solid was extracted with hot tolu-
ene and filtered, and the toluene was removed under vacuum to
afford the crude product. Upon recrystallization at –20 °C from an
acetonitrile solution, 3b was obtained as a pale yellow-orange pow-
3
(
3
The reaction mixture was stirred at 50 °C for 1 h and at room tem-
perature for an additional 4 d. After evaporation of the solvent, the
remaining black solid was dried under vacuum at 110 °C to remove
excessive iodine, washed with n-hexane and dried under vacuum to
yield the product (57%). C40
H 2.96, N 8.51; found C 24.97, H 2.97, N 8.40. H NMR
der (0.417 g, 0.60 mmol, 37%). C40
H 7.21, N 24.05; found C 68.33, H 7.23, N 23.56. H NMR
50
H N12 (698.91): calcd. C 68.74,
1
(
(
(
(
2 2
600.13 MHz, CD Cl ): δ = 7.14 (d, J = 7.2 Hz, 2 H, CHar.), 6.93
t, J = 7.8 Hz, 2 H, CHar.), 6.79 (d, J = 8.4 Hz, 2 H, CHar.), 6.66
d, J = 7.2 Hz, 2 H, CHar.), 6.53 (d, J = 7.2 Hz, 2 H, CHar.), 3.25
58 10
H I N12 (1976.02): calcd. C 24.31,
1
3
(
399.89 MHz, CD
3
CN): δ = 12.48 (s, 2 H, NH), 9.22 (d, J =
br. s, 16 H, CH
] ppm. 13C{ H} NMR (159.99 MHz, CD
C=N), 150.95 (C=N), 149.19 (Car.), 148.30 (Car.), 136.44 (Car.),
2
), 2.65 [s, 12 H, N(CH
3
)
2
], 2.62 [br. s, 12 H,
3
1
9.7 Hz, 4 H, H ), 7.39 (d, J = 9.6 Hz, 4 H, H ), 3.21 [s, 48 H,
N(CH
(
3
)
2
2
Cl ): δ = 151.13
2
ar.
ar.
4
+
N(CH
35.5 (100.0) [M – 10 I – H] , 352.3 (91.5) [M – 10 I – 2 H] . IR
CsI disc): ν˜ = 3020 (w), 2962 (w), 2930 (w), 2794 (w), 1616 (s),
526 (vs), 1465 (m), 1438 (m), 1402 (s), 1290 (s), 1207 (m), 1171
3 2
) ] ppm. MS (ESI+): m/z (%) = 176.7 (60.1) [M – 10 I] ,
3
+
2+
2
(
1
1
32.30 (Car.), 128.06 (CHar.), 125.29 (CHar.), 124.57 (Car.), 119.53
), 35.09 (CH
ppm. IR (CsI disc): ν˜ = 3032 (w), 2932 (m), 2845 (m), 1682 (s),
577 (vs), 1487 (m), 1438 (w), 1390 (m), 1279 (m), 1242 (m), 1011
(
CHar.), 117.26 (CHar.), 117.15 (CHar.), 48.90 (CH
2
3
)
–
1
(
m), 1169 (m), 1061 (w), 1034 (w), 896 (w), 828 (w) cm . UV/Vis
1
–
5
–1
–1
–1
–
1
3
(CH CN, c = 1.0ϫ10 molL ): λ (ε, Lmol cm ) = 208
(6.48ϫ10 ), 291 (1.96ϫ10 ), 364 (9.24ϫ10 ), 463 (4.04ϫ10 ), 488
(4.75ϫ10 ), 552 (1.33ϫ10 ), 596 (1.24ϫ10 ) nm.
(m), 960 (m), 833 (w), 763 (w), 697 (w) cm . MS (FAB): m/z (%)
4
5
4
4
2+
+
=
3
350.4 (42) [M + 2 H] , 699.8 (100) [M + H] . UV/Vis (CH CN,
4
4
4
–
5
–1
–1
–1
4
c = 1.17ϫ10 molL ): λ (ε, Lmol cm ) = 219 (8.32ϫ10 ), 237
4
4
(
7.56ϫ10 ), 358 (3.80ϫ10 ) nm.
(4a)H ](PF : To a solution of 3a dissolved in dry CH
20 mL) was added AgPF (70.8 mg, 0.28 mmol). After stirring at
[
(4b)H
in dry CH
(68.0 mg, 0.268 mmol) dissolved in dry CH
3
2
](I
3
)
3
I: To a solution of 3b (35.0 mg, 0.05 mmol) dissolved
CN (10 mL) was added dropwise a solution of iodine
CN (10 mL). The reac-
[
(
2
6
)
4
2
Cl
2
3
6
room temperature in the dark for 24 h, the reaction mixture was
tion mixture was stirred at 50 °C for 1 h and at room temperature
for an additional 4 d. After evaporation of the solvent, the remain-
ing black solid was dried under vacuum at 110 °C to remove excess
iodine, washed with n-hexane and dried under vacuum to yield the
filtered. The product was washed twice with dry CH (10 mL)
2
Cl
2
and dried under vacuum (87%). Crystals of [(4a)H ](PF ) suitable
2
6 4
2 2
for XRD studies were grown by diffusion of CH Cl into an aceto-
nitrile solution at room temperature. 1H NMR (399.89 MHz,
50 10
product (77%). C40H I N12 (1967.95): calcd. C 24.41, H 2.56, N
3
1
CD
3
CN): δ = 12.46 (s, 2 H, NH), 9.13 (d, J = 9.8 Hz, 4 H, Har.), 8.54; found C 24.48, H 2.62, N 8.35. H NMR (200.13 MHz,
3
3
7
.35 (d, J = 9.7 Hz, 4 H, Har.), 3.17 ppm [s, 48 H, N(CH
3
)
2
] ppm.
CD
3
CN): δ = 12.63 (s, 2 H, NH), 9.24 (d, J = 9.6 Hz, 4 H, Har.),
13
3
C NMR (150.92 MHz, CD
35.69, 128.49, 126.42, 123.42, 112.29, 41.85 (CH
CN): δ = –144.62 (sept) ppm. IR (CsI disc): ν˜ =
942 (w), 1637 (m), 1529 (m), 1471 (w), 1408 (m), 1371 (w), 1294
3
CN): δ = 161.49 (C=N), 156.98,
7.56 (d, J = 9.6 Hz, 4 H, Har.), 4.05 (br. s, 16 H, CH
2
), 3.04 [s, 24
CN): δ = 159.91
(C=N), 156.83, 135.98, 128.32, 123.56, 111.49, 49.80 (CH ), 34.74
) ppm. 3 P NMR H, N(CH
1
) ] ppm. C NMR (150.90 MHz, CD
13
1
3 3 2 3
(161.89 MHz, CD
3
2
4
+
2
3
(CH ) ppm. MS (ESI+): m/z (%) = 174.9 (5.5) [M – 10 I] , 232.7
3
+
2+
(
8
1
m), 1215 (w), 1172 (w), 1143 (m), 1064 (m), 1035 (w), 1008 (w), (78.0) [M – 10 I – H] , 348.3 (100.0) [M – 10 I – 2H] , 696.4
–1
+
39 (vs), 729 (m), 560 (s), 495 (m) cm . UV/Vis (CH
3
CN, c =
(55.0) [M – 10 I – 2 H] . IR (CsI disc): ν˜ = 3449 (m), 2967 (w),
.10ϫ10–5 molL ): λ (ε, Lmol cm ) = 212 (7.91ϫ10 ), 232 2925 (w), 2875 (w), 1593 (vs), 1546 (s), 1435 (w), 1414 (w), 1370
–1
–1
–1
4
Eur. J. Inorg. Chem. 2013, 163–171
169
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