C. Shimokawa et al.
Bull. Chem. Soc. Jpn. Vol. 79, No. 1 (2006)
119
X-ray Structure Determination. A single crystal was mount-
ed on a glass-fiber. Data of X-ray diffraction were collected by
a Rigaku RAXIS-RAPID imaging plate two-dimensional area
detector and a Rigaku AFC7/CCD mercury area detector using
diffusion of liquid methanol into a chloroform solution containing
NO ,HLDippH. IR (KBr): 3066 (NH), 1638 (C=N), 1573, 1304, 1279
2
cmꢁ1 (NO2); 1H NMR (CDCl3, 400 MHz): ꢄ 1.22 (24H, d, J ¼
6:8 Hz, CH3), 3.06 (4H, septet, J ¼ 6:8 Hz, CH), 7.18–7.28 (6H,
m, aromatic protons), 8.74 (2H, s, CH), 12.81 (1H, br, NH);
HRMS (EIþ): m=z 435.2883, calcd for C27H37N3O2 435.2886;
Anal. Calcd for C27H37N3O2: C, 74.45; H, 8.56; N, 9.65%. Found:
C, 74.72; H, 8.81; N, 9.41%.
ꢀ
graphite-monochromated Mo Kꢁ radiation (ꢂ ¼ 0:71070 A) to
2ꢃmax of 55.0ꢂ. All the crystallographic calculations were per-
formed using the Crystal Structure software package of the Molec-
ular Structure Corporation (version 3.6 and 3.7). The crystal struc-
tures were solved by direct methods and refined by full-matrix
least-squares using SIR-92 or SHELX97. All non-hydrogen atoms
and hydrogen atoms were refined anisotropically and isotropical-
ly, respectively. Crystallographic data have been deposited with
[CuI(NO ,HLDipp)(MeCN)] (3): To a methanol solution (2 mL)
2
containing NO ,HLDippH (43.7 mg, 0.1 mmol) and [CuI(MeCN)4]-
2
PF6 (37.3 mg, 0.1 mmol) was added triethylamine (10.1 mg, 0.1
mmol), and the mixture was stirred for 12 h at room temperature
in a glovebox ([O2] < 1 ppm and [H2O] < 1 ppm). The resulting
precipitates were collected by filtration and dried to give a yellow
powder in a 56% yield. Single crystals suitable for X-ray crys-
tallographic analysis were obtained by recrystallization from
an acetonitrile solution containing the complex at ꢁ40 ꢂC. IR
(KBr): 1605 (C=N), 1531, 1458, 1277 cmꢁ1 (NO2); 1H NMR
(DMSO-d6, 400 MHz): ꢄ 1.15 (12H, d, J ¼ 6:8 Hz, CH3), 1.22
(12H, d, J ¼ 6:8 Hz, CH3), 2.08 (3H, s, CH3), 3.24 (4H, septet,
J ¼ 6:8 Hz, CH), 7.19 (6H, m, aromatic protons), 8.61 (2H, s,
CH); HRMS (FABþ): m=z 498.2185, calcd for C27H37CuN3O2
498.2282; Anal. Calcd for C29H39CuN4O2: C, 64.60; H, 7.29; N,
10.39%. Found: C, 64.38; H, 7.33; N, 10.25%.
Cambridge Crystallographic Data Centre: Deposition numbers
CCDC-283079 for NO ,HLDippH, CCDC-283080 for Me,HLDipp
2
H
ꢃ
CH3OH, CCDC-283081 for [CuI(NO ,HLDipp)(CH3CN)] (3), CCDC-
283082 for [{CuI(CN,HLDep)}n] (6), CCDC-283083 for [{CuI-
CN,HLDipp)}n] (7), and CCDC-283084 for [{CuI(H,HLDipp)}2]
CH2Cl2 (9). Copies of the data can be obtained free of charge
Cambridge Crystallographic Data Centre, 12, Union Road, Cam-
bridge, CB2 1EZ, UK; Fax: +44 1223 336033; e-mail: deposit@
ccdc.cam.ac.uk).
2
(
ꢃ
Theoretical Calculations.
Heats of formation (ꢁHf) of
R1,R2LDippH were calculated using the PM3 semi-empirical molec-
ular orbital method.34 The calculations were performed using the
CAChe program version 3.2. Final geometries and energetics were
obtained by optimizing the total molecular energy with respect to
all structural variables.
[{CuI(CN,HLPh)}n] (4): Compound CN,HLPhH (24.7 mg, 0.1
mmol) in dichloromethane (1 mL) was added to a methanol solu-
tion (1 mL) of [CuI(MeCN)4]PF6 (37.3 mg, 0.1 mmol), and the
mixture was stirred for 12 h at room temperature. The resulting
precipitates were collected by filtration and dried to give a yellow
powder in a 95% yield. IR (KBr): 2203 (CꢅN), 1601 cmꢁ1 (C=
Synthesis.
phenyl)amino-2-methyl-2-propenimine (Me,HLDippH):
N-(2,6-Diisopropylphenyl)-3-(2,6-diisopropyl-
This
compound was prepared according to the reported procedure
with a little modification herein after described.35 To an ethanol
solution (50 mL) of 2,6-diisopropylaniline (5.32 g, 30 mmol) and
1,1,3,3-tetraethoxy-2-methylpropane (3.52 g, 15 mmol) was added
concentrated hydrochloric acid (1.25 mL, 15 mmol). The mixture
was refluxed for 24 h and then concentrated to give a brown res-
N); Anal. Calcd for C16H12CuN3 1/6H2O: C, 61.43; H, 3.97;
ꢃ
N, 13.43%. Found: C, 61.66; H, 3.85; N, 13.36%.
[{CuI(CN,HLMes)}n] (5): This compound was prepared in a
similar manner to that described for the synthesis of [{CuI-
(
CN,H Ph
CN,HLPh)}n] by using CN,HLMesH (33.1 mg, 0.1 mmol) instead of
L
H in a 83% isolated yield. IR (KBr): 2189 (CꢅN), 1647
idue. The crude product of Me,HLDippH HCl was neutralized with
cmꢁ1 (C=N); HRMS (FABþ): m=z 394.1347, calcd for C22H25-
CuN3 394.1344; Anal. Calcd for C22H24CuN3: C, 67.07; H,
6.14; N, 10.67%. Found: C, 66.89; H, 6.16; N, 10.57%.
ꢃ
a saturated sodium carbonate aqueous solution and the neutral li-
gand Me,HLDippH was extracted into dichloromethane (50 mL ꢄ 3).
The combined organic layer was dried over MgSO4. After remov-
al of MgSO4 by filtration, evaporation of the solvent gave a pale
brown material, from which Me,HLDippH was obtained as a white
powder by recrystallization from methanol in a 51% isolated
yield. Single crystals suitable for X-ray crystallographic analysis
were obtained by slow diffusion of liquid methanol into a chloro-
form solution containing Me,HLDippH. IR (KBr): 3169 (NH), 1638
[{CuI(CN,HLDep)}n] (6): This compound was prepared in a
similar manner to that described for the synthesis of [{CuI-
(
CN,HLPh)}n] by using CN,HLDepH (36.0 mg, 0.1 mmol) instead
of CN,HLPhH in a 73% isolated yield. Single crystals suitable
for X-ray crystallographic analysis were obtained by slow diffu-
sion at the interface between a methanol solution containing
[CuI(MeCN)4]PF6 and a dichloromethane solution containing
CN,HLDepH. IR (KBr): 2197 (CꢅN), 1647 cmꢁ1 (C=N); HRMS
(FABþ): m=z 422.1666, calcd for C24H29CuN3 422.1757; Anal.
Calcd for C24H28CuN3: C, 68.30; H, 6.69; N, 9.96%. Found: C,
68.49; H, 6.77; N, 9.96%.
1
cmꢁ1 (C=N); H NMR (CD3OD, 400 MHz): ꢄ 1.19 (24H, d, J ¼
6:8 Hz, CH3), 2.05 (3H, s, CH3), 3.20 (4H, septet, J ¼ 6:8 Hz,
CH), 6.67–7.24 (8H, m, aromatic protons and CH); HRMS
(EIþ): m=z 404.3195, calcd for C28H40N2 404.3191; Anal. Calcd
for C28H40N2 1/6H2O: C, 82.50; H, 9.97; N, 6.87%. Found: C,
82.58; H, 10.00; N, 6.80%.
N-(2,6-Diisopropylphenyl)-3-(2,6-diisopropylphenyl)amino-
[{CuI(CN,HLDipp)}n] (7):
a similar manner to that described for the synthesis of [{CuI-
(
CN,HLPh)}n] by using CN,HLDippH (41.6 mg, 0.1 mmol) instead
This compound was prepared in
ꢃ
2-nitro-2-propenimine (NO ,HLDippH): This compound was pre-
of CN,HLPhH in a 66% isolated yield. Single crystals suitable
for X-ray crystallographic analysis were obtained by slow diffu-
sion at the interface between a methanol solution containing
[CuI(MeCN)4]PF6 and a dichloromethane solution containing
CN,HLDippH. IR (KBr): 2193 (CꢅN), 1647 cmꢁ1 (C=N); HRMS
(FABþ): m=z 478.2283, calcd for C28H37CuN3 478.2283; Anal.
Calcd for C28H36CuN3: C, 70.33; H, 7.59; N, 8.79%. Found: C,
70.03; H, 7.66; N, 8.73%.
2
pared by applying the following reported procedure.36 2,6-Di-
isopropylaniline (5.32 g, 30 mmol) was added to a methanol solu-
tion (100 mL) of 1-methyl-5-nitro-1H-pyrimidin-2-one (2.33 g, 15
mmol). The mixture was refluxed for 96 h. After the reaction,
evaporation of the solvent gave a brown oily material, from which
NO ,HLDippH was isolated in a 21% yield by flash SiO2 column
2
chromatography with chloroform as the eluent. Single crystals
suitable for X-ray crystallographic analysis were obtained by slow
[{CuI(CN,MeLDipp)}n] (8): To a methanol solution (2 mL) con-