Paper
NJC
tt
tt
[
Ce(Cp )
2
(l-I)]
2
(3). A Schlenk flask was charged with KCp
Engineering and Physical Sciences Research Council (grant
(0.82 g, 4 mmol) and [Ce(I)
3
(THF) ] (1.62 g, 2 mmol). The flask numbers EP/K039547/1 and EP/L014416/1).
4
was cooled to ꢀ78 1C and THF (15 ml) was added dropwise with
stirring. The yellow reaction mixture was allowed to slowly warm
to room temperature and then stirred for a further 16 hours. The
mixture was allowed to settle for 2 hours and the suspension was
filtered. Volatiles were removed in vacuo (10 mbar), affording a
bright orange solid. The solid residue was extracted with toluene
Notes and references
ꢀ
2
1 G. Wilkinson and J. M. Birmingham, J. Am. Chem. Soc., 1954,
76, 6210.
(
8 ml) and stored at room temperature, affording 3 as an orange
2 (a) S. Arndt and J. Okuda, Chem. Rev., 2002, 102, 1953;
(b) F. T. Edelmann and V. Lorenz, Coord. Chem. Rev., 2000,
209, 99.
1
crystalline product (0.30 g, 24%). H NMR (d
6
-benzene, 298 K):
tt
d = ꢀ5.86 (br m, 6H, Cp -CH), ꢀ1.71, (br s, 72H, C(CH ) ), 0.29
3
3
tt
tt
(s, 2H, Cp -CH), 1.13 (s, 4H, Cp -CH). Anal calcd (%) for
C H Ce I : C, 50.24; H, 6.81. Found (%): C, 49.88; H, 6.68. m
eff
3 (a) M. R. MacDonald, J. E. Bates, J. W. Ziller, F. Furche and
W. J. Evans, J. Am. Chem. Soc., 2013, 135, 9857; (b) W. J. Evans,
J. Alloys Compd., 2009, 488, 493; (c) W. J. Evans, Inorg. Chem.,
2007, 46, 3435; (d) M. C. Cassani, D. J. Duncalf and M. F.
Lappert, J. Am. Chem. Soc., 1998, 120, 12958; (e) W. J. Evans,
S. L. Gonzales and J. W. Ziller, J. Am. Chem. Soc., 1991, 113, 7423.
4 (a) M. V. Butovskii, B. Oelkers, T. Bauer, J. M. Bakker,
V. Bezugly, F. R. Wagner and R. Kempe, Chem. – Eur. J., 2014,
20, 2804; (b) M. V. Butovskii, C. D ¨o ring, V. Bezugly, F. R.
Wagner, Y. Grin and R. Kempe, Nat. Chem., 2010, 2, 741;
(c) M. V. Butovskii, O. L. Tok, F. R. Wagner and R. Kempe,
Angew. Chem., Int. Ed., 2008, 47, 6469; (d) I. P. Beletskaya,
A. Z. Voskoboynikov, E. B. Chuklanova, N. I. Kirillova, A. K.
Shestakova, I. N. Parshina, A. I. Gusev and G. K. I. Magomedov,
J. Am. Chem. Soc., 1993, 115, 3156.
5 For other ligand systems see: (a) M. P. Blake, N. Kaltsoyannis
and P. Mountford, Chem. Commun., 2013, 49, 3315; (b) P. L.
Arnold, J. Mc Master and S. T. Liddle, Chem. Commun., 2009,
818; (c) S. T. Liddle, Proc. R. Soc. A, 2009, 465, 1673.
6 (a) D. Patel and S. T. Liddle, Rev. Inorg. Chem., 2012, 32, 1;
(b) S. T. Liddle and D. P. Mills, Dalton Trans., 2009, 5592.
7 See, for example: (a) S. P. Green, C. Jones and A. Stasch,
Science, 2007, 318, 844; (b) T. Nguyen, A. D. Sutton,
M. Brynda, J. C. Fettinger, G. J. Long and P. P. Power,
Science, 2005, 310, 1754; (c) I. Resa, E. Carmona,
E. Gutierrez-Puebla and A. Monge, Science, 2004, 305, 1136.
8 (a) L. Maron, E. L. Werkema, L. Perrin, O. Esienstein and
R. A. Andersen, J. Am. Chem. Soc., 2005, 127, 2792;
(b) G. R. Giesbrecht, G. E. Collis, J. C. Gordon, D. L. Clark,
B. L. Scott and N. J. Hardman, J. Organomet. Chem., 2004,
689, 2177; (c) Z. Xie, K. Chui, Q. Yang, T. C. W. Mak and
J. Sun, Organometallics, 1998, 17, 3937; (d) E. B. Lobkovsky,
Yu. K. Gun’ko, B. M. Bulychev, V. K. Belsky, G. L. Soloveichik
and M. Yu. Antipin, J. Organomet. Chem., 1991, 406, 343;
(e) W. J. Evans, J. M. Olofson, H. Zhang and J. L. Atwood,
Organometallics, 1988, 7, 629.
5
2
84 2 2
ꢀ
1
(
Evans method, 298 K, d
n = 1250 (m), 1201 (w), 1165 (m), 1089 (w), 1054 (br m), 1021 (m),
19 (s), 810 (s), 767 (m).
6 B
-benzene): 2.23 m . FTIR (Nujol, cm ):
8
0
0 0
0 00
[
Ce(Cp )(I)
2 2
(THF) ] (4). A THF (20 ml) solution of KCp
(
1.60 g, 5 mmol) was added dropwise to a THF (15 ml) slurry of
[
Ce(I) (THF) ] (4.05 g, 5 mmol) at ꢀ4 1C with stirring. A colour
3
4
change to yellow with a white precipitate was observed, and the
mixture was slowly warmed to room temperature and stirred for
7
2 hours. Volatiles were removed in vacuo, yielding a bright
yellow powder. The solid was extracted with hexane (20 ml) and
volatiles were removed in vacuo (10 mbar), affording 4 as a
yellow powder (2.39 g, 58%). A small crop of crystals were grown
ꢀ2
1
from hexanes (2 ml) at ꢀ25 1C. H NMR (d
6
-benzene, 298 K):
0
0 0
d = ꢀ3.74 (s, 18H, Si(CH ) ), ꢀ0.03 (s, 1H, Cp -CH), 0.27 (s, 1H,
3
3
0
0 0
Cp -CH), 0.76 (s, 9H, Si(CH ) ), 2.25 (br m, 16H, THF). Anal
3
3
calcd (%) for C H CeI O Si : C, 32.23; H, 5.53. Found (%):
C, 32.08; H, 5.61. meff (Evans method, 298 K, d
m
1
2
2
45
2
2
3
6
-benzene): 2.41
. FTIR (Nujol, cm ): n = 1260 (m), 1249 (m), 1092 (br m),
019 (br m), 934 (w), 837 (br s), 723 (w).
ꢀ
1
B
0
0 0
00 0
[
Ce(Cp
toluene (20 ml) solution of [KN(SiMe
added dropwise to a toluene (20 ml) solution of 4 (4.10 g,
mmol) at ꢀ20 1C with stirring. The reaction mixture was warmed
)
2
(I)(THF)] (5) and [Ce(Cp ){N(SiMe
3 2 2
) } ] (6). A
3 2
)
] (1.00 g, 5 mmol) was
5
to room temperature and stirred for 16 hours, forming a dark
orange mixture with a white precipitate. The suspension was
filtered, the solution concentrated to 5 ml and cooled to 4 1C,
yielding orange crystals of 5. More crops of 5 were obtained from the
supernatant liquid of the first crystallisation (2.36 g, 50%). From the
third recrystallization several crystals with different morphologies
were observed. These were identified as [Ce(N{SiMe } ) ] (orange
3
2 3
needles) and 6 (orange blocks) via single crystal X-ray studies. Data
1
0 00
for 5: H NMR (d -benzene, 298 K) d = ꢀ5.75 (s, 2H, Cp -CH),
6
0
00
ꢀ
5.34 (br s, 2H, Cp -CH), 0.30 (s, 36H, Si(CH
Si(CH ). meff (Evans method, 298 K, d -benzene): 2.22 m
calcd (%) for C28 58CeISi : C, 42.64; H, 7.27. Found: C, 42.72;
H, 7.38 (%). FTIR (Nujol, cm ): n = 1249 (s), 1090 (s), 986 (s),
35 (m), 837 (br s), 753 (m).
3
)
3
), 0.90 (s, 18H,
3
)
3
6
B
. Anal
H
6
9 (a) T. Mehdoui, J.-C. Berthet, P. Thu ´e ry and M. Ephritikhine,
Dalton Trans., 2005, 1263; (b) T. Mehdoui, J.-C. Berthet, P. Thu ´e ry
and M. Ephritikhine, Chem. Commun., 2005, 2860; (c) P. N.
Hazin, C. Lakshminarayan, L. S. Brinen, J. L. Knee, J. W.
Bruno, W. E. Streib and K. Folting, Inorg. Chem., 1988,
ꢀ
1
9
2
7, 1393; (d) M. D. Walter, D. Bentz, F. Weber, O. Schmitt,
G. Wolmersh ¨a user and H. Sitzmann, New J. Chem., 2007, 31, 305.
We thank the EPSRC and The University of Manchester for 10 (a) M. P. Coles, P. B. Hitchcock, M. F. Lappert and
generously supporting this work. This work was funded by the A. V. Protchenko, Organometallics, 2012, 31, 2682;
Acknowledgements
New J. Chem.
This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2015