Full Paper
5
,6-Bis-(N,N’-dimethyl-N,N’-ethylene-guanidino)-2,2-dimeth-
(12733), 450 (3255) nm; Crystal data for [1a](PF
6
)
2
: M
=666.45,
r
3
0
8
.40ꢂ0.30ꢂ0.15 mm , monoclinic, space group P2 /n, a=
yl-[1,3]-benzodioxole (4)
1
.1660(16) ꢁ, b=12.125(2) ꢁ, c=28.503(6) ꢁ, b=97.72(3)8, V=
A suspension of CH CN (20 mL) and 5,6-diamino-2,2-dimethyl-1,3-
3
ꢀ3
3
6244.96 ꢁ , Z=12, d =1.580 Mgm , 2q=3.66 to 60.128, Mo
c
a
l
c
d
K
a
benzodioxole dihydrochloride (0.878 g, 3.469 mmol) was cooled
with ice. A solution of 2-chloro-1,3-dimethyl-4,5-dihydro-1H-imida-
zolium chloride (9 mL, 0.961m, 8.671 mmol, 2.5 equiv) was added
radiation (graphite-monochromated, l=0.71073 ꢁ), T=100 K,
measured reflections 16150, independent 8220, R =0.0415, final
int
2
R indices [I>2s(I)]: R (F)=0.052, wR (F )=0.148.
1
2
to this suspension. NEt (4.9 mL, 10 equiv) was added to the result-
3
ing red solution. The reaction was slowly warmed up and stirred
for 5 h. A methanolic solution of NaOMe (3.9 mL, 5.4m, 6 equiv)
was added to the filtered solution. Shortly afterward, the solvent
was removed and the residue treated with water (10 mL). After 2 h
of stirring, the precipitated product was isolated by filtration. The
product was dried over Na SO and extracted with Et O. Solvent
4
(PF ) ·CH CN
6 2 3
Compound 4 (50.1 mg, 0.135 mmol) was dissolved in CH CN
3
(5 mL). FcPF6 (89.0 mg, 0.269 mmol) was added to the solution.
The resulting orange solution was stirred at room temperature for
16 h. Then, the solvent was removed under vacuum. The residue
was washed with 4ꢂ3 mL Et O. Then, it was dissolved in CH CN
2
4
2
residues were extricated with n-hexane from the product. After sol-
vent removal, pale-yellow solid was obtained (0.940 g,
.573 mmol, 73% yield). Crystals were grown from Et O solution at
2
3
a
(3 mL) and the solution was filtered. This solution was overlaid by
2
2
Et O (36 mL). The crystalline orange product (83.2 mg, 0.118 mmol,
88% yield) was isolated by filtration and washed with 2ꢂ2.5 mL
Et O. Elemental analysis calcd (%) for C H F N O P ·CH CN
(703.47 gmol ): C 35.86, H 4.44, N 13.94; found: C 35.98, H 4.04, N
14.34; H NMR (399.89 MHz, CD CN): d=6.13 (s, 2H, H , H ), 3.85
(m, 8H, -NCH -), 2.78 (s, 12H, -MMe), 1.96 (s, 3H, CH CN), 1.82 (s,
2 3
6
2
ambient conditions. Elemental analysis calcd (%) for C H N O
19
30
6
2
ꢀ
1
(
2
372.46 gmol ): C 61.27, H 7.58, N 22.56; found: C 61.35, H 7.60, N
2
19 28 12
6
2
2
3
1
2.86; H NMR (399.89 MHz, CD Cl ): d=6.16 (s, 2H, H ), 3.16 (s,
ꢀ1
2
2
ar
13
8
H,-NCH -), 2.60 (s, 12H, -MMe), 1.59 (s, 6H, -CMe) ppm; C NMR
1
2
3
C3
C6
(
150.90 MHz, CD Cl , HSQC, HMBC): d=154.0 (C7, C12), 141.6 (C1,
2 2
C2, C4, C5), 134.9 (C1, C2, C4, C5), 116.6 (-CMe), 103.4 (C3, C6), 48.9
13
H, -CMe) ppm; C NMR (100.55 MHz, CD CN, HSQC, HMBC): d=
3
+
(
(
-NCH -), 34.9 (-NMe), 25.6 (-CMe) ppm; HR-MS (ESI , CH OH): m/z
2 3
163.8 (C7, C12), 128.5 (-CMe), 49.8 (-NCH -), 33.0 (-NMe), 25.8 (-CMe)
ppm; no signals found for C1–C6; F NMR (376.23 MHz, CD CN):
2
+
%)=373.23464 (100) [M+H] ; IR (CsI): n=2988 (w), 2933 (w),
19
3
2
1
843 (w), 1655 (s), 1605 (m), 1482 (s), 1441 (w), 1412 (m), 1390 (m),
352 (w), 1281 (m), 1245 (m), 1215 (m), 1189 (m), 1140 (s), 1072
31
d=ꢀ72.86 (d, J=706.6 Hz) ppm; P NMR (161.88 MHz, CD CN):
3
d=ꢀ144.63 (sept, J=706.6 Hz) ppm; IR (CsI): n=3091 (w), 2950
(
(
w), 1035 (s), 969 (s), 891 (s), 846 (s), 805 (s), 788 (m), 730 (s), 712
(
(
w), 2910 (w), 2255 (w), 1636 (s), 1606 (s), 1558 (w), 1473 (w), 1414
s), 1367 (m), 1301 (m), 1259 (s), 1217 (s), 1157 (w), 1087 (w), 1024
ꢀ1
m), 663 (m), 625 (m), 545 (w), 514 (m), 471 (w), 407 (m) cm ; UV/
ꢀ
5
ꢀ1
ꢀ1
Vis (CH CN, c=2.214ꢂ10 m, d=1 cm): l (e in lmol cm )=220
(
3
(w), 982 (w), 838 (vs), 785 (m), 694 (w), 652 (w), 558 (s), 503 (w)
cm
lmol cm )=225 (27488), 300 (12733), 450 (3255) nm; Crystal
data for 4(PF ) ·CH CN: M =703.47, 0.21ꢂ0.04ꢂ0.03 mm , ortho-
rhombic, space group Pbca, a=14.8644(4) ꢁ, b=18.2389(6) ꢁ, c=
21.3201(6) ꢁ, V=5780.1(3) ꢁ , Z=8, d
to 67.68, CuKa radiation (l=1.54184 ꢁ), T=120 K, measured reflec-
tions 152345, independent 5195, R =0.1393, final R indices [I>
ꢀ1
shoulder), 277 (9823), 336 (13212) nm; CV in CH Cl , (100 mVs ):
ꢀ1
ꢀ4
2
2
;
UV/Vis (CH CN, c=1.560ꢂ10 m, d=0.2 cm):
l
(e in
3
ꢀ
ꢀ
E1/2 =ꢀ0.46 (rev. 1e , ꢀ0.37/ꢀ0.55), ꢀ0.33 (rev. 1e , ꢀ0.27/ꢀ0.39)
ꢀ1
ꢀ1
3
V; Crystal data for 4·H O: M =390.49, 0.60ꢂ0.40ꢂ0.30 mm , mono-
3
2
r
6
2
3
r
clinic, space group P2 /c, a=8.022(16) ꢁ, b=13.315(3) ꢁ, c=
1
3
1
1
8.984(4) ꢁ,
b=97.51(3)8,
V=2010.3(7) ꢁ ,
Z=4,
dcalcd
=
3
ꢀ3
=1.617 Mgm , 2q=4.1
calcd
ꢀ
3
.290 Mgm , 2q=3.7 to 61.18, Mo radiation (graphite-monochro-
Ka
mated, l=0.71073 ꢁ), T=100 K, measured reflections 11386, inde-
pendent 5813, R =0.0680, final R indices [I>2s(I)]: R (F)=0.053,
int
2
int
1
2s(I)]: R(F)=0.056, wR(F )=0.149.
2
wR (F )=0.141.
2
[
3(CuCl2)]
3
(PF6)2
Compound 1 (54.1 mg, 0.147 mmol) was dissolved in diethyl ether
(3 mL). To this solution, anhydrous CuCl2 (18.8 mg, 0.140 mmol,
0.95 equiv) was added and stirred for 2 days. The green precipitate
was isolated by filtration and washed with diethyl ether (2 mL). Re-
leased from solvent remnants in vacuo 68.8 mg (0.134 mmol) of
the product was obtained, which corresponds to 96% yield. Crys-
tals were grown by slow diffusion of n-hexane into THF. Elemental
Compound 3 (51.4 mg, 0.137 mmol) was dissolved in CH CN
3
(
5 mL). FcPF (90.4 mg, 0.274 mmol) was added to the yellow solu-
6
tion. The resulting orange-colored solution was mixed at room
temperature for 5 h. Then, the solvent was removed under
vacuum. The residue was washed with 2ꢂ2 mL toluene and 4ꢂ
4
mL n-hexane. The residue was dissolved in CH CN (3 mL) and the
3
ꢀ
1
solution was filtered. Then, this solution was overlaid by Et O
analysis calcd (%) for C H Cl CuN O (510.95 gmol ): C 44.66, H
17 32 2 6 2
2
(
18 mL). The crystalline orange product (50.1 mg, 0.075 mmol, 55%
6.31, N 16.45; found: C 44.31, H 6.06, N 16.49; HR-MS (FAB, NPOE):
+
63
37
+
yield) was isolated by filtration and washed with 2ꢂ2 mL Et O. Ele-
mental analysis calcd (%) for C H F N O P (666.43 gmol ): C
3
m/z (%)=377.3 (100) [L+H] , 513.1244 (22.4) [L+ Cu L ] and
2
2
ꢀ1
65
37 35
65
35
+
63
37 35
+
[L+ Cu L Cl], 511.1242 (62.4) [L+ Cu L ] and [L+ Cu L Cl]
2
1
9
32 12
6
2
2
1
63
35
+
65
37
+
4.24, H 4.84, N 12.61; found: C 34.73, H 4.76, N 12.98; H NMR
, 509.1266 (54.3) [L+ Cu L ] , 478.1580 (12.7) [L+ Cu Cl] ,
2
476.1589 (58.6) [L+ Cu Cl] and [L+ Cu Cl] , 474.1593 (74.9)
65
35
+
63
37
+
(
399.89 MHz, CD CN): d=6.01 (s, 2H, H , H ), 3.02 (s, 24H, -NMe),
3
C3
C6
13
63
35
+
1
.82 (s, 6H, -CMe) ppm; C NMR (100.55 MHz, CD CN, HSQC,
[L+ Cu Cl] ; IR (CsI): n=3074 (w), 2998 (w), 2983 (w), 2935 (m),
2886 (w), 2790 (w), 1586 (m), 1546 (m), 1515 (m), 1488 (m), 1464
(w), 1400 (s), 1331 (m), 1275 (m), 1229 (m), 1166 (s), 1137 (m), 1105
(w), 1066 (m), 1020 (m), 981 (s), 935 (w), 916 (m), 894 (s), 857 (m),
816 (m), 803 (m), 784 (w), 731 (w), 702 (w), 629 (w), 512 (w), 486
3
HMBC): d=165.9 (C7, C12), 161.1 (C1, C2, C4, C5), 159.8 (C1, C2,
C4, C5), 127.8 (-CMe), 97.3 (C3, C6), 42.3 (-NMe), 25.8 (-CMe) ppm;
1
9
F NMR (376.23 MHz, CD CN): d=ꢀ72.84 (d, J=706.6 Hz) ppm;
3
3
1
P NMR (161.88 MHz, CD CN): d=ꢀ144.64 (sept, J=706.6 Hz)
3
ꢀ
1
ꢀ4
ppm; IR (CsI): n=2957 (w), 1621 (s), 1590 (m), 1520 (w), 1473 (w),
1
1
7
1
(w) cm ; UV/Vis (CH CN, c=5.010ꢂ10 m, d=0.2 cm): l (e in
3
ꢀ1
ꢀ1
408 (s), 1311 (m), 1292 (w), 1261 (m), 1221 (m), 1191 (w), 1176 (w),
lmol cm )=233 (21001), 324 (12493), 410 (1968, shoulder), 755
ꢀ1
ꢀ
158 (w), 1093 (w), 1070 (w), 1024 (w), 986 (w), 838 (vs), 782 (m),
(637) nm; CV (CH Cl , 100 mVs ): E=ꢀ0.26 E (Cu) (irrev. 1e ),
2
2
ox
ꢀ
1
ꢀ ꢀ
05 (w), 672 (w), 558 (s), 503 (w), 471 (w) cm ; UV/Vis (CH CN, c=
ꢀ1.04 E (Cu) (irrev. 1e ), ꢀ0.12 (rev. 1e , ꢀ0.06/ꢀ0.18), 0.36 (rev.
3
red
ꢀ4
ꢀ1
ꢀ1
ꢀ
.068ꢂ10 m, d=0.2 cm): l (e in lmol cm )=225 (27488), 300
1e , 0.29/0.43) V. Crystals grown from Et O solution: crystal data
2
&
&
Chem. Eur. J. 2016, 22, 1 – 14
10
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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