Iron and Nickel Complexes Containing β-Diketiminato Ligands
1581 s, 1530 vs, 1496 vs, 1459 vs, 1436 vs, 1425 vs, 1378 s, 1362 s, 1348 s,
1318 m, 1278 vs, 1266 vs, 1187 vs, 1164 m, 1127 m, 1070 s, 1039 s, 1026 s,
965 w, 951 w, 924 m, 855 w, 801 w, 774 w, 755 vs, 737 s, 697 m, 680 m, 638 w,
597 w, 560 w, 541 w, 455 w, 440 w, 415 w.
the structures were solved by direct methods (SHELXS-97) [6] and
refined versus F2 (SHELXL-97) [7] with anisotropic temperature
factors for all non-hydrogen atoms (Table 1). All hydrogen atoms
were added geometrically and refined by using a riding model. Un-
fortunately in the case of 3 the low quality of the crystals obtained
did not allow for better values R1 and wR2 and resulted in residual
electron density in the final Fourier map.
[LFeCl] (1): 2.5 mL of a 1.6 M solution of n-butyllithium in n-hex-
ane (0.004 mol) were added to a yellow solution of 1.370 g II
(0.004 mol) in 10 mL of thf cooled to Ϫ78 °C. After annealing to
r.t. the yellow solution was added slowly (within 20 min.) to a sus-
pension of 0.507 g (0.004 mol) FeCl2 in thf. After stirring for 2 h
the solvent was removed under vacuum and the resulting red resi-
due was washed with 5 mL of n-hexane. Afterwards it was extracted
with n-hexane/CH2Cl2 (1:10), and filtering followed by removal of
the volatiles yielded 0.710 g of crude 1. After recrystallisation from
n-hexane/thf (1:10) 0.620 g (0.002 mol, 36 %) of pure 1 was
obtained in form of red crystals. Elemental analysis for
C19H21ClFeN2S2 (432.81 gmolϪ1); C 52.58 (calc. 52.73); H 5.11
(4.89); N 6.44 (6.47); Cl 8.69 (8.19) %.
Table 1. Crystal data and experimental parameters for the crystal
structure analyses for 1, 2 and 3.
1·1/2 OEt2
2
3
molecular formula
C42H52Cl2Fe2N4OS4 C20H21F3FeN2O3S3 C19H21BrN2NiS2
formular weight /g·molϪ1 939.72
546.43
480.11
temperature /K
crystal system
space group
150(2)
monoclinic
P21/n
15.260(2)
6.6058(5)
21.608(3)
150(2)
triclinic
P-1
210(2)
monoclinic
P21/n
15.265(2)
6.6423(5)
21.790(3)
˚
a /A
10.6840(6)
11.1039(6)
23.912(2)
100.560(4)
93.250(4)
118.214(4)
2423.5(3)
4
˚
b /A
Single crystals could be obtained by cooling a concentrated diethyl-
˚
c /A
ether solution to 4 °C for 2 days.
α /deg
β /deg
IR (KBr) /cmϪ1: 3057 w, 2965 w, 2923 w, 1533 s, 1458 vs, 1428 s, 1371 vs,
1358 vs, 1283 s, 1195 m, 1130 w, 1097 w, 1067 w, 1027 m, 939 m, 864 w,
804 w, 782 w, 753 s, 739 m, 711 w, 656 w, 629 w, 551 w, 491 w, 466 w, 419 w,
327 m, 302 w. μeff ϭ 4.95 B.M. (29 °C).
94.934(11)
94.272(11)
γ /deg
3
˚
V /A
2170.1(4)
2
1.438
1.022
980
2203.2(5)
4
1.447
2.888
976
Z
densitiy /g·cmϪ3
μ(MoKα) /mmϪ1
F(000)
1.498
0.928
1120
[LFeOTf] (2): 0,53 mL of a 1.6 M solution of n-butyllithium in n-
hexane (0.80 mmol) were added to a yellow solution of 274 mg II
(0.80 mmol) in 10 mL thf cooled to Ϫ78 °C. After annealing to r.t.
the yellow solution was added slowly (within 20 min.) to a colour-
less solution of 349 mg [Fe(OTf)2(MeCN)2] (0.80 mmol) in thf.
After stirring for 2 h the solvent was removed under vacuum, and
the resulting red residue washed with 5 mL of n-hexane. Afterwards
it was extracted three times with 7 mL diethylether, and after con-
centration and cooling 80 mg (0.15 mmol, 18 %) of 2 were obtained
in form of red crystals. Elemental analysis for C20H21F3FeN2O3S3
(546.43 gmolϪ1); C 43.77 (calc. 43.96); H 4.04 (3.87); N 4.99
(5.13) %.
GooF
1.163
1.101
1.173
R1 [I>2σ(I)]
wR2 (all data)
Δρmax / Δρmin /e·A
0.0799
0.1939
0.810 / Ϫ0.747
0.0374
0.0855
0.818 / Ϫ0.518
0.1183
0.3145
1.922 / Ϫ1.322
Ϫ3
˚
Crystallographic data for the structures of 1, 2 and 3 have been
deposited with the Cambridge Crystallographic Data Centre as
supplementary publication no. 697485 (1), 697484 (2), 697486 (3).
Copies of the data can be obtained free of charge on application
to The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ,
UK (Fax: (ϩ44) 1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk).
Single crystals could be obtained bei cooling a concentrated
diethylether solution to 4 °C for 2 days.
IR (KBr) /cmϪ1: 3052 w, 2979 w, 2917 w, 1637 w, 1578 w, 1521 m, 1458 s,
1436 s, 1381 vs, 1315 s, 1278 vs, 1262 s, 1239 s, 1186 s, 1127 w, 1029 s, 972 w,
865 w, 828 w, 754 m, 734 m, 636 m, 516 w, 454 w, 425 w.
Results and Discussion
Syntheses of Mononuclear Fe and Ni Complexes Containing
L
[LNiBr] (3): 2.5 mL of a 1.6 M solution of n-butyllithium in n-
hexane (0.004 mol) were added to a yellow solution of 1.370 g II
(0.004 mol) in 10 mL thf cooled to Ϫ78 °C. After annealing to r.t.
the yellow solution was added slowly (within 20 min.) to a suspen-
sion of 1.235 g [NiBr2dme] (0.004 mol) in thf. After stirring for 2 h
the solvent was removed under vacuum, and the resulting brown-
green residue washed with 10 mL of Et2O. Afterwards it was dis-
solved with 10 ml CH2Cl2 and after concentration followed by
cooling (4 °C) 0.820 g (0.002 mol, 40 %) of pure 3 were obtained in
form of dark green crystals suitable for X-ray diffraction analysis.
Elemental analysis for C19H21BrN2NiS2 (480.11 gmolϪ1); C 47.19
(calc. 47.53); H 4.87 (4.41); N 5.48 (5.83); Br 16.88 (16.64) %.
Trying to reproduce the synthesis reported for I [3] it was
found that the reaction of acetylacetone with 2-amino-
thiophenol in ethanol does not lead to the red crystalline
solid described which had been identified as I by means of
NMR-spectroscopy and elemental analysis (Scheme 1). In
contrast to the literature statements the two compounds
IR (KBr) /cmϪ1: 3058 w, 2988 w, 2965 w, 2918 w, 1523 s, 1449 vs, 1434 vs,
1413 s, 1361 vs, 1308 s, 1281 vs, 1267 vs, 1230 s, 1192 s, 1157 s, 1128 m,
1065 m, 1033 s, 1020 s, 968 m, 957 w, 942 m, 861 w, 833 w, 779 w, 772 m,
752 s, 742 s, 729 s, 698 m, 667 w, 659 w, 631 w, 561 w, 549 w, 523 w, 490 w,
473 w, 458 w, 422 w, 396 w, 355 w, 328 w, 309 w, 268 w. μeff ϭ 2.73 B.M
(24 °C).
Crystal Structure Determinations
The data of 1, 2 and 3 were collected on a Stoe IPDS 2T dif-
fractometer using MoKα radiation, λ ϭ 0.71073 A. In all cases,
Scheme 1. Reaction of acetylacetone with 2-aminothiophenol in
toluene does not lead to the β-diketimine I.
˚
Z. Anorg. Allg. Chem. 2009, 312Ϫ316
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
313