Bis(1-phenyl-1,2-ethenedithiolato)nickel(0)
Organometallics, Vol. 15, No. 26, 1996 5667
([S2C2Ph(C4H6N)]+, 44.6), 223 ([NiS2C2Ph]+, 28.8), 207 ([S2C2-
Ph(C3H6)]+, 42.6), 206 ([S2C2PhC3H5]+, 13.8). Anal. Found:
C, 54.43; H, 4.36; N, 5.10. Calcd for C24H22N2NiS4: C, 54.86;
H, 4.22; N, 5.33.
Ta ble 2. Cr ysta l Da ta for 1
empirical formula
fw
C16H12S4Ni
391.21
temp
23(1) °C
wavelength
cryst syst
space group
unit cell dimens
0.710 69 Å
monoclinic
Id en t ifica t ion of (1-p h en yl-1,2-et h en ed it h iola t o)[1-
ph en yl-2-(1-cyan ocycloh exyl)-1,2-eth en edith iolato]n ickel-
(0) (3b): deep blue crystals; mp 128-129.2 °C. 1H NMR
(CDCl3): δ 1.59-1.88, 2.11-2.39 (m, 10H, C6H10), 7.42-7.59
(m, 8H and 5H H in Ph adjacent to the substituent and H of
m- and p-positions of Ph adjacent to H), 8.00 (d, J ) 7.33 Hz,
2H, H o-position of Ph adjacent to H), 10.3 (s, 1H, H in the
nickeladithiolene ring). 13C NMR (CDCl3): δ 23.07, 24.65,
38.35, 46.65 (C6H10), 119.30 (CN), 126.83, 126.90, 128.16,
129.27, 129.38, 129.59, 130.40, 139.96 (Ph), 166.77, 170.55 (J CH
) 169.7 Hz, CH in the nickeladithiolene ring), 176.51, 180.09
(C in the nickeladithiolene ring). Mass (70 eV): m/ z 497 (M+,
3.4), 390 (M+ - C6H10CN + H, 100), 290 ([NiS2C2Ph(H)S2H2]+,
21), 273 ([S2C2Ph(H)(C6H10CN)]+, 34.4), 236 ([Ni(S2C2H)2]+,
75.3), 224 ([Ni(S2CPh(H)]+, 32.9). Anal. Found: C, 55.87; H,
5.03; N, 3.06. Calcd for C23H21NNiS4: C, 55.43; H, 4.25; N,
2.81.
P21/c (No. 14)
a ) 9.420(3) Å
b ) 9.579(3) Å
c ) 17.844(2) Å
â ) 106.70(2)°
γ ) 91.61(2)°
1609.5(7) Å3, 4
1.61 g/cm3
V, Z
D(calcd)
abs coeff, µ(Mo KR)
F(000)
cryst size
radiation
scan type
2θmax for data collection
no. of rflns collected
no. of indep rflns
refinement method
no. of data/params
goodness of fit on F
final R indices (I > 3σ(I))
largest diff peak and hole
17.12 cm-1
800.00
0.10 × 0.13 × 0.50 mm
Mo KR (λ ) 0.710 69 Å)
ω-2θ
55.0°
3280
3054
full-matrix least squares
1043/241
1.19
Id en tifica tion of bis[1-p h en yl-2-(1-cya n ocycloh exyl)-
1,2-eth en ed ith iola to]n ick el(0) (4b): deep purple crystals;
mp 270.8-271.0 °C. 1H NMR (CDCl3): δ 1.57-1.86, 2.11-
2.86 (m, 20H, C6H10), 7.42-7.56 (m, 10H, Ph). 13C NMR
(CDCl3): δ 23.04, 24.60, 38.33, 47.13 (C6H10), 118.96 (CN),
128.16, 128.98, 129.76, 140.12 (Ph), 180.54, 184.11 (C in the
nickeladithiolene ring). Mass (70 eV): m/ z 604 (M+, 0.63),
R ) 0.039, Rw ) 0.026
0.32 and -0.31 e-/Å3
and converged (largest parameter was 0.16 times its esd) with
unweighted and weighed agreement factors of
395 (M+ - C2(Ph)(C6H10CN), 0.18), 331 ([NiS2C2Ph(C6H10
-
CN)]+, 0.57), 273 ([SC(Ph)C(C6H10CN)]+, 65.9), 246 ([SC(Ph)C-
(C6H9)]+, 11). Anal. Found: C, 59.02; H, 5.43; N, 4.57. Calcd
for C30H30N2NiS4: C, 59.51; H, 4.99; N, 4.63.
R )
||Fo| - |Fc||/ |Fo| ) 0.039
∑
∑
Rw ) [ w(|Fo| - |Fc|)2/ w|Fo| ]1/2 ) 0.026
2
∑
∑
Id en t ifica t ion of (1-p h en yl-1,2-et h en ed it h iola t o)[1-
p h en yl-2-(1-cya n o-1,3-d im eth ylbu tyl)-1,2-eth en ed ith iola -
to]n ick el(0) (3c): deep blue crystals; mp 50.5-52 °C. 1H
NMR (CDCl3): δ 1.93 (s, 3H, CH3CCN), 1.90 (dd, J ) 14.04,
5.5 Hz, 1H, HCH), 2.25 (dd, J ) 14.04, 5.5 Hz, 1H, HCH),
1.69-1.87 (m, 1H, Me2CH), 0.97 (d, J ) 6.71 Hz, 3H, CH3CH-
(CH3)), 0.83 (d, J ) 6.10 Hz, 3H, CH3CH(CH3)). 13C NMR
(CDCl3): δ 23.43, 23.64, 26.06 (Me), 30.80, 45.16, 50.89 (C in
side chain), 121.26 (CN), 126.80, 128.07, 129.22, 129.38,
129.65, 130.44, 138.49, 139.96 (Ph), 170.90 (J CH, 172.1 Hz, C
having H in the nickeladithiolene ring), 175.50 (C in the
nickeladithiolene ring), 178.63, 189.29 (C in the nickeladithi-
olene ring). Anal. Found: C, 55.50; H, 5.48; N, 2.76. Calcd
for C23H23NNiS4: C, 55.21; H, 4.63; N, 2.80.
All calculations were performed using the teXsan crystal-
lographic software package of Molecular Structure Corp.
Crystal data and details of the X-ray experiments are given
in Table 2.
Rea ction of Nick ela d ith iolen e 1 w ith Azo Com p ou n d s.
The complex 1 (ca. 0.3 mmol) and azo compound 2 (ca 0.3
mmol) were reacted in benzene (100 cm3) under reflux for 22
h under an Ar atmosphere.
The products were separated by column chromatography
using silica gel (Wako-gel C-300). The eluent was a mixture
of hexane and dichloromethane. Chromatography afforded
satisfactorily pure product.
Id en tifica tion of bis[1-p h en yl-2-(1-cya n o-1,3-d im eth -
ylbu tyl)-1,2-eth en edith iolato]n ickel(0) (4c): deep blue crys-
tals; mp 153.5-154.6 °C. 1H NMR (CDCl3): δ 1.94 (s, 3H,
CH3CCN), 1.90 (dd, J ) 14.04, 6.71 Hz, 1H, HCH), 2.25 (dd, J
) 14.04, 5.5 Hz, 1H, HCH), 1.67-1.86 (m, 1H, Me2CH), 0.97
(d, J ) 6.71 Hz, 3H, CH3CH(CH3)), 0.83 (d, J ) 6.71 Hz, 3H,
CH3CH(CH3)). 13C NMR (CDCl3): δ 23.43, 23.64, 26.06 (Me),
30.80, 45.16, 50.89 (C in side chain), 121.26 (CN), 126.80,
128.07, 129.22, 129.38, 129.65, 130.44, 138.49, 139.96 (Ph),
170.90 (J CH, 172.1 Hz, C having H in the nickeladithiolene
ring), 175.50 (C in the nickeladithiolene ring), 178.63, 189.29
(C in the nickeladithiolene ring). Anal. Found: C, 58.59; H,
5.50; N, 4.66. Calcd for C30H34N2NiS4: C, 59.11; H, 5.62; N,
4.60.
Id en t ifica t ion of (1-p h en yl-1,2-et h en ed it h iola t o){1-
p h en yl-2-[1-(m et h oxyca r b on yl)et h yl]-1,2-et h en ed it h io-
la to}n ick el(0) (3d ): deep blue crystals; mp 135 °C. 1H NMR
(CDCl3): δ 1.76 (s, 6H, Me), 3.35 (s, 3H, OMe), 7.32 (dd, J )
6.10, 1.83 Hz, 2H, H at o-position of Ph adjacent to the
substituent), 7.38-7.55 (m, 6H, H in Ph at the m- and
p-positions), 8.00 (dd, J ) 6.72, 1.83 Hz, 2H, H at o-position
of Ph adjacent to H), 9.82 (s, 1H, H in the nickeladithiolene
ring). 13C NMR (CDCl3): δ 28.93 (Me), 52.09 (OMe), 126.84,
127.85, 128.88, 129.16, 129.22, 129.97, 138.61,140.25 (Ph),
167.80, 174.34 (C in the nickeladithiolene ring), 181.04 (COO),
186.05, 186.32 (C in the nickeladithiolene ring). Mass (70
Identification of (1-phenyl-1,2-ethenedithiolato)[1-phenyl-
2-(1-cyano-1-methylethyl)-1,2-ethenedithiolato]nickel(0) (3a ):
deep blue crystals; mp 135 °C. UV-vis (benzene): 318 (ꢀ
44 000), 576 (1900), 796 nm (28 000). 1H NMR (CDCl3): δ 1.91
(s, 6H, Me), 7.44-7.66 (m, 8H, H in Ph at the m- and
p-positions), 8.02 (m, 2H, H at the o-position of Ph adjacent to
H), and 10.05 (s, 1H, H in the nickeladithiolene ring). 13C
NMR (CDCl3): δ 30.5 (Me), 40.0 (CMe2), 121.7 (CN), 126.84,
126.89, 128.23, 128.95, 129.23, 129.41, 129.68, 130.49, 138.47,
139.98 (Ph), 170.98 (J CH ) 173.4 Hz, CH in the nickel
dithiolene ring), 175.70, 179.42, 189.40 (C in the nickeladithi-
olene ring). Mass (70 eV): m/ z 457 (M+, 29.3), 390 (M+
-
C4H6N+H, 11.5), 288 ([Ni(S2C2Ph(H))S2]+, 31.5), 233 ([S2C2-
Ph(C4H6)]+, 41.4), 224 ([Ni(S2C2Ph(H)]+, 21.1), 218 ([S2C2(Ph)-
(C3H3N)]+, 30.2). Anal. Found: C, 52.93; H, 3.78; N, 3.23.
Calcd for C20H17NNiS4: C, 52.41; H, 3.74; N, 3.06.
Id en tifica tion of bis[1-p h en yl-2-(1-cya n o-1-m eth yleth -
yl)-1,2-eth en ed ith iola to]n ick el(0) (4a ): deep purple crys-
tals; mp 237.8-239.5 °C. UV-vis (benzene): 321 (ꢀ 49 000),
579 (2400), 776 nm (27 000). 1H NMR (CDCl3): δ 1.91 (s, 12H,
Me), 7.37-7.62 (m, 10H, H in Ph). 13C NMR (CDCl3): δ 30.51
(Me), 40.52 (CMe2), 121.29 (CN), 128.28, 128.95, 129.90, 140.05
(Ph), 180.23, 183.93 (C in the nickeladithiolene ring). Mass
(70 eV): m/ z 524 (M+, 95.9), 457 (M+ - C4H6N+H, 15.2), 355
(M+ - C4H6C2Ph, 12.9), 291 (M+ - S2C2Ph(H), 45.2), 233