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Data collection was done on a Bruker AXS Ultra TXS rotating anode
CCD instrument using an Oxford Cryosystems series 700 N cryostat.
Data collection and reduction was done using the Bruker AXS APEX2
Notes and references
2
a
Department of Chemistry, University of Bergen, Allégaten 41, N-5007,
20
Bergen, Norway.
suite programs. Structure solution and refinement was done using
b
21
75 programs SHELXS and SHELXL, respectively. CCDC codes 904595
Institut für Anorganische Chemie, Eberhard Karls Universität
5
Tübingen, Auf der Morgenstelle 18, D-72076, Tübingen, Germany. Fax:
(2) and 904596 (3) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
+49 7071 292436; E-mail:reiner.anwander@uni-tuebingen.de
†
Electronic Supplementary Information (ESI) available: Experimental
details, NMR and FTIR data presented. See DOI: 10.1039/b000000x/
8
0
1
2
Metal And Metalloid Amides (Herausg.: M. F. Lappert, P. P. Power,
A. R. Sanger, R. C. Srivastava), Ellis Horwood, Chichester, 1980.
a) W. A. Herrmann, R. Anwander, F. C. Munck, W. Scherer, V.
Dufaud, N. W. Huber and G. R. J. Artus, Z. Naturforsch., 1994, 49B,
1789-1797; b) R. Anwander, O. Runte, J. Eppinger, G. Gerstberger,
E. Herdtweck and M. Spiegler, J. Chem. Soc., Dalton Trans., 1998,
847-858; c) W. A. Herrmann, F. C. Munck, G. R. J. Artus, O. Runte
and R. Anwander, Organometallics, 1997, 16, 682-688; d) C.
Meermann, G. Gerstberger, M. Spiegler, K. W. Törnroos and R.
Anwander, Eur. J. Inorg. Chem., 2008, 2014-2023.
For initial silylamine elimination reactions, see: O. Runte, T.
Priermeier and R. Anwander, Chem. Commun., 1996, 1385-1386; b)
J. Eppinger, M. Spiegler, W. Hieringer, W. A. Herrmann and R.
Anwander, J. Am. Chem. Soc., 2000, 122, 3080-3096.
For initial silylamide elimination reactions, see: a) I. Nagl, M.
Widenmeyer, E. Herdtweck, G. Raudaschl-Sieber and R. Anwander,
Microporous Mesoporous Mater., 2001, 44-45, 311-319; b) M. G.
Klimpel, R. Anwander, M. Tafipolsky and W. Scherer,
Organometallics, 2001, 20, 3983-3992.
1
1
2
0
5
0
Synthesis of Ce[N(SiHMe
in THF (10 ml) was added to a solution of PhICl
2 2 4
) ] 2: A solution of 1 (0.266 g, 0.390 mmol)
18
2
(0.053 g, 0.193 mmol)
in THF (2 ml) in one portion in the dark. A colour change from yellow to
red was observed immediately. This solution was allowed to stir for 1 hr.
The volatiles were removed via vacuum leaving an oily solid. To this,
hexane (2 ml) was added and upon subsequent cooling to –35 °C dark red
crystals suitable for X-ray diffraction were produced (yield 20%). In pure
form, 2 can be sublimed at 80 °C/1.2×10 mbar. IR (DRIFT): vmax = 2953
m, 2900 w, 2102 m, 2009 m, 1942 vw sh, 1419 vw, 1248 s, 1020 s, 939 s,
85
90
95
-
4
-
1
8
89 vs, 841 s, 795 s, 768 m, 746 vw, 679 m, 631 w, 586 m, 409 w cm .
3
4
1
H NMR (400 MHz, [D
Si(H)Me ), 6.01 (septet, J = 2.9 Hz, 8H, Si(Me
Si : C, 28.71; H, 8.43; N, 8.37. Found: C, 28.30; H, 7.88; N,
6
]benzene, 20 °C): σ = 0.34 (d, J = 7.4 Hz, 48H,
2
2
)H). Anal. Calc. for
C
16
H
56CeN
4
8
6
.43%.
Alternative synthesis of Ce[N(SiHMe
(0.099 g, 0.35 mmol) in toluene (3 ml) was slowly added to a solution of
(0.241 g, 0.35 mmol) in toluene (3 ml). A colour change from yellow to
red was observed immediately. This solution was allowed to stir for
.5 hr. The volatiles were removed via vacuum leaving a dark red solid
0.327 g). To this, toluene (0.5 ml) was added and upon subsequent 100
2 2 4
) ] 2: A solution of trityl chloride
2
3
3
4
4
5
5
5
0
5
0
5
0
5
1
0
(
5
A. F. England, PhD Thesis, The Thorium Benzyne and the
Cerium(IV)-Nitrogen Bond, Massachusetts Institute of Technology,
1995.
C. Morton, N. W. Alcock, M. R. Lees, I. J. Munslow, C. J. Sanders
and P. Scott, J. Am. Chem. Soc., 1999, 121, 11255-11256.
a) O. Eisenstein, P. B. Hitchcock, A. G. Hulkes, M. F. Lappert and L.
Maron, Chem. Commun., 2001, 1560-1561; b) P. B. Hitchcock, A. G.
Hulkes, M. F. Lappert, Inorg. Chem., 2004, 43, 1031-1038.
P. L. Arnold, Z. R. Turner, N. Kaltsoyannis, P. Pelekanaki, R. M.
Bellabarba and R. P. Tooze, Chem. Eur. J., 2010, 16, 9623-9629.
M. P. Coles, P. B. Hitchcock, A. V. Khvostov, M. F. Lappert, Z. Li
and A. V. Protchenko, Dalton Trans., 2010, 39, 6780-6788.
cooling to -40 °C dark red crystals of 2 suitable for X-ray diffraction were
produced (along with colourless crystals of Gomberg’s dimer). Yield
calculated from NMR data (based on the Ce-content): 60%.
6
7
Second alternative synthesis of Ce[N(SiHMe
2
)
2
]
4
2: A solution of
hexachloroethane (0.174 g, 0.73 mmol) in toluene (5 ml) was slowly 105
added to a solution of 1 (1.001 g, 1.47 mmol) in toluene (5 ml). A colour
change from yellow via orange and bright red to dark red occurred within
8
9
1
8 hr, after which the volatiles were removed via vacuum leaving dark
red sticky crystals (0.954 g). To this, toluene (1.5 ml) was added and upon
subsequent cooling to -40 °C dark red crystals of 2 suitable for X-ray 110
diffraction were produced A solution of hexachloroethane (0.045 g, 0.19
mmol) in toluene (2 ml) was slowly added to a solution of 1 (0.257 g,
10 P. B. Hitchcock, M. F. Lappert and A. V. Protchenko, Chem.
Commun., 2006, 3546-3548.
0
.38 mmol) in toluene (5 ml). A colour change from yellow via orange
11 P. Dröse, A. R. Crozier, S. Lashkari, J. Gottfriedsen, S. Blaurock, C.
G. Hrib, C. Maichle-Mössmer, C. Schädle, R. Anwander and F. T.
Edelmann, J. Am. Chem. Soc., 2010, 132, 14046–14047.
12 E. d. L. Jiménez, S. Javed and D. M. Hoffman, Inorg. Chim. Acta,
2009, 362, 385-388.
and bright red to dark red occurred within 18 hr, after which the volatiles
were removed via vacuum leaving dark red sticky crystals (0.240 g). To
this, toluene (0.5 ml) was added and upon subsequent cooling to –40 °C
dark red crystals of 2 suitable for X-ray diffraction were produced (yield
of two crops combined: 0.116 g, 0.17 mmol, 45%).
115
13 S. M. Mansell, B. F. Perandones and P. L. Arnold, J. Organomet.
Chem., 2010, 695, 2814-2821.
19
Synthesis of Ce[N(SiHMe
2 2 8 7
) ] Cl 3: A solution of 1a (0.488 g, 0.910
mmol) in toluene (10 ml) was added to a solution of PhICl
2
(0.125 g, 120 14 W. J. Evans, D. S. Lee, D. B. Rego, J. M. Perotti, S. A. Kozimor, E.
0.454 mmol) in toluene (2 ml) in one portion in the dark. A colour change
from yellow to red was observed immediately. This solution was allowed
to stir for 1 hr. The volatiles were removed via vacuum leaving an oily
solid. To this, hexane (2 ml) was added and upon subsequent cooling to -
K. Moore and J. W. Ziller, J Am. Chem. Soc., 2004, 126, 14574-
14582.
15 I. Nagl, W. Scherer, M. Tafipolsky and R. Anwander, Eur. J. Inorg.
Chem., 1999, 1405-1407.
5 °C colourless crystals suitable for X-ray diffraction were produced 125 16 a) G. B. Deacon, T. Feng, S. Nickel, B. W. Skelton and A. H. White,
3
(yield 38%). IR (DRIFT): vmax = 2952 m, 2898 w, 2123 m sh, 2066 m,
J. Chem. Soc., Chem. Commun., 1993, 1328-1329; b) G. B. Deacon,
T. Feng, P. C. Junk, B. W. Skelton, A. N. Sobolev and A. H. White,
Aust. J. Chem., 1998, 51, 75-89.
2
008 m sh, 1959 m sh, 1910 m sh, 1418 w, 1296 w sh, 1254 m, 1057 m
sh, 1024 m sh, 1008 m sh, 959 m, 893 s, 837 m, 795 m, 769 m, 687 m,
1
5
2
91 m, 565 w, 410 m. H NMR (400 MHz, [D
6
]benzene, 20 °C): δ = 0.12,
17 C. Meermann, K. W. Törnroos, W. Nerdal and R. Anwander, Angew.
Chem. Int. Ed., 2007, 46, 6508-6513.
.11, 4.71. Anal. Calc. for C32 Cl Si16: C, 19.15; H, 5.63; N,
H
112Ce
5
7
N
8
130
6
6
7
0
5
0
5.59. Found: C, 17.53; H, 4.44; N, 4.57%.
Crystal data for 2: C16 Si , M = 669.49, monoclinic, a =
8.3037(9) Å, b = 11.1158(5) Å, c = 18.8563(9) Å, β = 107.559(1) °, V =
18 A. Baranowski, D. Plachta, L. Skulski and M. Klimaszewska, J.
Chem. Res. (S), 2000, 435-437.
‡
H
56CeN
4
8
1
2
9
0
H. F. Yuen and T. J. Marks, Organometallics, 2008, 27, 155-158.
Bruker (2008); SMART, SAINT, SADABS and XPREP. Area detector
control and data integration and reduction software. Bruker
Analytical X-ray Instruments Inc., Madison, WI, USA.
1
3
3
1
657.8(3) Å , T = 103(2) K, space group P2 /c, Z = 4, 65647 reflections
135
measured, 12241 independent reflections (Rint = 0.0443). R
0.0243 (I > 2σ(I)), wR(F ) = 0.0662 (all data).
1
values =
2
2
1
G. M. Sheldrick, Acta. Cryst. 2008, A64, 112-122.
§
5 7 8
Crystal data for 3: C32H112Ce Cl N Si16, M = 2007.49, monoclinic, a =
1
8
7.2810(6) Å, b = 25.5225(9) Å, c = 19.8095(7) Å, β = 100.2028(4)°, V =
598.9(5) Å , T = 100(2) K, space group C2/c, Z = 4, 71792 reflections
3
measured, 12787 independent reflections (Rint = 0.0292). R
0.0210 (I > 2σ(I)). wR(F ) values = 0.0549 (all data).
1
values =
2
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