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Fedushkin et al.
which was prepared in situ from tmsꢀBIAN (0.32 g, 1 mmol) and
metallic sodium (0.023 g, 1 mmol) in diethyl ether (30 mL). The
color of the solution changed from green to brown. Then the
diethyl ether was removed, benzene was added, and the solution
was filtered off from the precipitate of NaI. Brown crystals
of 3 were isolated from the concentrated solution. The yield was
hermuller, K. Wieghardt, P. Chaudhuri, Dalton Trans.,
2003, 3483.
3. P. Ghosh, E. Bill, T. Weyhermüller, K. Wieghardt, J. Am.
Chem. Soc., 2003, 125, 3967.
4. (a) S. C. Bart, E. J. Hawrelak, A. K. Schmisseur, E. Lobꢀ
kovsky, P. J. Chirik, Organometallics, 2004, 23, 237; (b) S. C.
Bart, E. J. Hawrelak, E. Lobkovsky, P. J. Chirik, Organoꢀ
metallics, 2005, 24, 5518; (c) M. M. Khusniyarov, E. Bill,
T. Weyhermüller, E. Bothe, K. Harms, J. Sundermeyer,
K. Wieghardt, Chem. Eur. J., 2008, 14, 7608; (d) M. M.
Khusniyarov, T. Weyhermüller, E. Bill, K. Wieghardt, Anꢀ
gew. Chem., Int. Ed., 2008, 47, 1228; (e) N. Muresan, C. C.
Lu, M. Ghosh, J. C. Peters, M. Abe, L. M. Henling,
T. Weyhermüller, E. Bill, K. Wieghardt, Inorg. Chem., 2008,
47, 4579; (f) B. Weber, E, Kaps, Heteroatom. Chem., 2005,
16, 391; (g) B. L. Small, R. Rios, E. R. Fernandez, M. J.
Carney, Organometallics, 2007, 26, 1744; (h) M. M. Khusꢀ
niyarov, T. Weyhermüller, E. Bill, K. Wieghardt, J. Am.
Chem. Soc., 2009, 131, 1208; (i) N. Muresan, T. Weyꢀ
hermüller, K. Wieghardt, Dalton Trans., 2007, 4390;
(j) R. R. Kapre, E. Bothe, T. Weyhermüller, S. DeBeer
George, N. Muresan, K. Wieghardt, Inorg. Chem., 2007,
46, 7827.
0
.24 g (68%), m.p. 270 C. Found (%): C, 66.48; H, 6.82.
–
1
C H FeN Si (M = 861 g mol ). Calculated (%): C, 66.90;
H, 6.97. IR, /cm : 1603 w, 1592 w, 1499 s, 1480 s, 1403 m,
4
8
60
4
4
–
1
1
357 m, 1250 s, 1153 w, 1134 w, 1107 m, 1015 m, 946 s, 838 s,
7
65 s, 676 s, 615 w, 557 w.
1
,2ꢀBis[(trimethylsilyl)imino]acenaphthene iron diiodide (4).
A solution of iron diiodide, which was prepared in situ from
iodine (0.25 g, 1 mmol) and an excess of metallic iron in diethyl
ether (20 mL), was added to a solution of tmsꢀBIAN (0.32 g,
1
mmol) in diethyl ether (20 mL). The color of the solution
changed from orange to brown. Then the diethyl ether was reꢀ
moved, and benzene was added. Compound 4 was isolated as
brown crystals by concentrating the solution. The yield was
0
.40 g (56%), m.p. 225 C. Found (%): C, 40.14; H, 4.11.
–
1
C24H30FeI N Si (M = 712.33 g mol ). Calculated (%):
C, 40.43; H, 4.21. IR, /cm–1: 1630 m, 1619 m, 1584 m, 1419 w,
2
2
2
1
257 s, 1219 w, 1161 w, 1076 w, 1030 m, 930 m, 849 s, 830 s,
7
80 m, 753 w, 676 s, 537 w.
[
5. (a). M. P. Shaver, L. E. N. Allan, V. C. Gibson, Organoꢀ
metallics, 2007, 26, 4725; (b) V. C. Gibson, R. K. O´Reilly,
D. F. Wass, A. J. P. White, D. J. Williams, Macromolecules,
2003, 36, 2591; (c) L. E. N. Allan, M. P. Shaver, A. J. P.
White, V. C. Gibson, Organometallics, 2007, 21, 8963.
6. P. Le Floch, F. Knoch, F. Kremer, F. Mathey, J. Scholz,
W. Scholz, K.ꢀH. Thiele, U. Zenneck, Eur. J. Inorg. Chem.,
1998, 119.
Tris(1,2ꢀdiiminoacenaphthenide)]ironꢀbis(iron tribromide
tetrahydrofuranate) (5). tmsꢀBIAN (0.32 g, 1 mmol), FeBr2•
2H O (0.25 g, 1 mmol), and THF (20 mL) were placed in
•
2
a tube. The color of the solution changed from orange to green.
Darkꢀgreen crystals of 5 were isolated from the solution within
4
C, 44.20; H, 4.02. C H Br Fe N O (M = 1614.20 g mol ).
Calculated (%): C, 44.61; H, 4.09. IR, /cm : 3150 m, 1607 w,
1
8 h. The yield was 0.37 g (70%), m.p. 163 C Found (%):
–
1
6
0
66
6
3
6
6
–
1
7. B. L. Small, M. Brookhart, J. Am. Chem. Soc., 1998,
120, 7143.
553 w, 1442 s, 1415 m, 1342 w, 1080 m, 1061 m, 1034 s, 914 m,
8
22 s, 772 m, 591 w, 541 w, 519 m. Compound 5 was characterꢀ
8. R. J. Trovitch, E. Lobkovsky, E. Bill, P. J. Chirik, Organoꢀ
metallics, 2008, 27, 1470.
ized by magnetochemical measurements.
Xꢀray diffraction studies of compounds 1—5. The Xꢀray difꢀ
fraction data sets were collected on a Bruker AXS SMART APEX
diffractometer (—ꢀscanning technique, MoꢀK radiation,
9. B. M. Schmiege, M. J. Carney, B. L. Small, D. L. Gerlach,
J. A. Halfen, Dalton Trans., 2007, 2547.
10. I. L. Fedushkin, A. A. Skatova, V. A. Chudakova, G. K.
Fukin, Angew. Chem., Int. Ed., 2003, 42, 3294.
= 0.71073 Å, graphite monochromator) at 100 (for 1—4) and
1
50 K (for 5). Absorption corrections were applied using the
11. (a) M. M. Khusniyarov, K. Harms, O. Burghaus, J. Sunderꢀ
meyer, Eur. J. Inorg. Chem., 2006, 2985; (b) I. L. Fedushkin,
V. M. Makarov, V. G. Sokolov, G. K. Fukin, Dalton Trans.,
2009, 8047.
2
1
SADABS program. The structures were solved by direct methꢀ
ods using the SHELXS97 program2 and refined by the fullꢀ
matrix leastꢀsquares method based on F
2
2
using the SHELXL97
hkl
program.23 All nonhydrogen atoms were refined with anisotroꢀ
pic displacement parameters. The hydrogen atoms were placed
in idealized positions and refined using a riding model. The strucꢀ
tures were deposited with the Cambridge Crystallographic Data
Centre (CCDC 930236, 930237, 930240, 930238, and 930239
for 1, 2, 3, 4, and 5, respectively).
12. (a) N. Muresan, C. C. Lu, M. Ghosh, J. C. Peters, M. Abe,
L. M. Henling, T. Weyhermuller, E. Bill, K. Wieghardt,
Inorg. Chem., 2008, 47, 4579; (b) M. M. Khusniyarov,
T. Weyhermuller, E. Bill, K. Wieghardt, Angew. Chem., Int.
Ed., 2008, 47, 1228.
13. I. L. Fedushkin, V. A. Chudakova, G. K. Fukin, S. Dechert,
M. Hummert, H. Schumann, Russ. Chem. Bull. (Int. Ed.),
2004, 53, 2744 [Izv. Akad. Nauk, Ser. Khim., 2004, 2634].
14. I. L. Fedushkin, A. A. Skatova, V. A. Chudakova, V. K.
Cherkasov, S. Dechert, H. Schumann, Russ. Chem. Bull.
This study was financially supported by the Russian
Foundation for Basic Research (Project Nos 11ꢀ03ꢀ97057p
and 13ꢀ03ꢀ00542).
(
2
Int. Ed.), 2004, 53, 2142 [Izv. Akad. Nauk, Ser. Khim.,
004, 2051].
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5. I. L. Fedushkin, V. A. Chudakova, A. A. Skatova, G. K.
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