E. Carmona et al.
1
13
1
1
1
2
1.0; H NMR (500 MHz, C
2H; Me), 1.97 ppm (s, 12H; Me); C-{ H} NMR (125 MHz, C
58C): d=ꢀ0.3 (SiMe ), 11.1 (C-Me), 15.2 (C-Me), 55.6 (C-SiMe ), 133.9
6
D
6
, 258): d=0.01 (s, 18H; SiMe
3
), 1.83 (s,
2H; CH); C{ H } NMR (125 MHz, C
6
D
6
, 258C): d=ꢀ0.2 (SiMe
3
), 9.9
1
3
1
6
D
6
,
(CH
3
-Cp*), 69.7 (CSiMe
3
), 108.1 (C
5
Me
5
), 111.6 (CH), 123.0 ppm (CH).
5
1
3
3
Synthesis of iminoacyls [Zn(h -C
Me
R)(h -C(C
Me
R)NXyl)], (8 and
5
4
5
[20]
4
(
C-Me), 136.8 ppm (C-Me).
Synthesis of [Zn(C SiMe
and ZnCl (0.47 g, 3.47 mmol) were dissolved in THF (30 mL) and stirred
at room temperature for 12 h. After evaporation of the solvent, the resi-
due was extracted with pentane (2ꢌ20 mL). The yellow solution was con-
9
): The C
5
Me
5
derivative 10 has been reported. Compounds 8 (R=H)
) were generated by the reaction of equimolar amounts
[
12a]
5
H
4
3
)
2
] (1):
LiC
5
H
4
SiMe
3
(1.00 g, 6.93 mmol)
and 9 (R=SiMe
3
of 2 and 5 (0.5–0.7 mmol), respectively, with CNXyl in hexane, at room
temperature for a period of 4–5 h. Iminoacyls 8 and 9 were crystallised in
pentane or hexane and isolated in about 90% yield.
2
5
1
centrated and left at ꢀ208C until crystals suitable for X-ray analysis were
5 4 5 4
[Zn(h -C Me H)(h -C(C Me H)NXyl)] (8): Yield: 95%; elemental analy-
sis calcd (%): C 73.9, H 8.0, N 3.2; found: C 73.5, H 8.0, N 3.2; IR
(nujol): n˜ =1585 cm (C=N); H NMR (300 MHz, C D , 258C): d=1.62
6 6
(s, 6H; C-Me), 1.72 (s, 6H; C-Me),1.82 (s, 6H; C-Me), 1.90 (s, 6H; C-
Me), 1.99 (s, 6H; C-Me), 3.54 (s, 1H; CH), 5.12 (s, 1H; CH) 6.80 (t, 1H;
), 7.03 (d, 2H; H
Me ), 11.5 (Me ), 12.1 (h -Me
(CH), 96.7 (h -CH), 128.7 (CH
N), 202.2 ppm (C=N).
1
obtained. Yield: 0.60 g (51%); H NMR (500 MHz, C
6
D
6
, 258C): d=0.05
1
3
1
ꢀ1
1
(
s, 18H; SiMe
NMR (125 MHz, C
17.7 ppm (CH).
Synthesis of [Zn(C
1.51 mmol) and ZnCl
mixture of diethyl ether and toluene (80 mL) in a 250 mL thick-walled
glass ampoule equipped with Teflon screw cap (Young valve). The reac-
tion mixture was heated at 1158C under vacuum for 48 h. After evapora-
tion of solvents the residue was extracted with hexane (2ꢌ30 mL) and
crystallised from the same solvent. Yield: 2.13 g (60%); elemental analy-
3
), 6.26 (s, 4H; CH), 6.6131 ppm (s, 4H; CH); C-{ H}
6
D
6
, 258C): d=ꢀ0.2 (SiMe ), 87.2 (C-Si), 117.5 (CH),
3
1
[
16]
13
1
5
Me
4
H)
2
]
(2): Octamethylmagnesocene
(1.57 g,
H
p
m 6 6
); C{ H} NMR (75 MHz, C D
, 258C): d=9.7 (h -
), 19.3 (Me-CNXyl), 73.6
-Me), 128.0 (CH ), 156.2 (C
5
5
1
2
(3.07 g, 11.51 mmol) were dissolved in of a 1:1
a
a
b
), 13.6 (Me
), 123.5 (C
b
5
m
q
p
q
-
5
1
[Zn(h -C Me SiMe )(h -C(C Me SiMe )NXyl)] (9): Yield 85%; elemental
analysis calcd (%): C 67.99, H 8.75, N 2.40; found: C 67.7, H 8.7, N 2.6;
IR (nujol): n˜ =1580 cm (C=N); H NMR (400 MHz, C D , 258C): d=
3 3
0.22 (s, 9H; SiMe ), 0.23 (s, 9H; SiMe ), 1.69 (s, 6H; C-Me), 1.73 (s, 6H;
5
4
3
5
4
3
ꢀ1
1
6
6
1
sis calcd (%): C 70.3, H 8.5; found: C 69.7, H 8.6; H NMR (300 MHz,
C
6
D
6
, 258C): d=1.84 (s, 6H; C-Me), 1.95 (s, 6H; C-Me), 4.31 ppm (s,
C-Me),1.84 (s, 6H; C-Me), 1.91 (s, 6H; C-Me), 2.12 (s, 6H; C-Me), 6.48
(t, 1H; H ), 7.00 ppm (d, 2H; H ); C-{ H} NMR (100 MHz, C D ,
p m 6 6
1
3
1
13
1
1
H; CH); C-{ H} NMR (75 MHz, C
C-Me), 73.7 (CH), 118.7 (C-Me), 120.8 ppm (C-Me).
Synthesis of [Zn(C Me tBu)) (3), [Zn(C Me SiMe
Zn(C Me SiMe ] (5): These compounds were prepared by reaction of
ZnCl and MCp’ in THF, at room temperature, for a period of about 3 h
M=K, Cp’=C
M=K, Cp’=C Me
6
D
6
, 258C): d=10.4 (C-Me), 12.6
(
258C): d=ꢀ1.9 (SiMe ), 2.1 (SiMe ), 9.9 (C-Me), 11.5 (C-Me) 12.4 (C-
3
3
3 3
Me), 14.2 (C-Me), 19.5 (C-Me), 75.9 (C-SiMe ), 96.4 (C-SiMe ), 115.5 (C-
5
4
2
]
5
4
2 2
tBu) ] (4) and
Me), 117.6 (C-Me), 122.7 (C-H), 126.1 (C-Me), 128.7 (C-H), 134.6 (C-
Me), 139.1 (C-Me), 156.1 (C-N), 201.2 ppm (C=N).
[
5
4
3 2
)
2
[
53]
[54]
(
5
Me
4
tBu for 3; M=Li, Cp’=C
5
Me
4 2
SiMe tBu for 4;
[
52b]
5
4
SiMe
3
for 5; ). After removal of the volatiles in
vacuo the residue was dissolved in hexane and the solutions filtered. Par-
tial evaporation of the solvent and cooling at ꢀ208C afforded crystals of
the corresponding zincocenes in good isolated yields (ca. 70–80%). Ana-
lytical and spectroscopic data for these compounds are listed below.
Acknowledgements
[
Zn(C
5 4 2
Me tBu) ] (3): Yield: 78%; elemental analysis calcd (%): C 74.40,
Financial support from the Spanish Ministerio de Educaciꢄn y Ciencia
1
H 10.11; found: C 74.4, H 10.3; H NMR (400 MHz, C
6
D
6
, 258C): d=1.51
(
0
MEC) (project CTQ2007-62814 and Consolider-Ingenio 2010 CSD2007-
0006) and the Junta de Andalucꢁa (project FQM672) is gratefully ac-
1
3
1
(
(
6
s, 9H; C-tBu), 1.94 (s, 6H; C-Me), 2.10 (s, 6H; C-Me); C-{ H} NMR
100 MHz, C , 258C): d= 11.3 (C-Me), 15.5 (C-Me), 32.8 (C-Me ),
7.8 (C-Me ), 100.2 (C-tBu), 118.0 (C-Me), 120.8 ppm (C-Me).
Zn(C Me SiMe tBu) ] (4): Yield: 70%; elemental analysis calcd (%): C
7.23, H 10.07; found: C 67.3, H 9.9; H NMR (300 MHz, C
tBu), 0.79 (s, 9H; SiMe tBu), 1.99 (s, 6H; C-Me),
.11 ppm (s, 6H; C-Me); C-{ H} NMR (75 MHz, C
, 258C): d=ꢀ0.9
SiMe tBu), 11.1 (C-Me), 14.3 (C-Me), 20.7 (C-Me ), 26.9 (C-Me ), 76.7
C-Si), 122.8 (C-Me), 125.1 ppm (C-Me).
Zn(C Me SiMe ] (5): Yield: 80%; elemental analysis calcd (%): C
3.69, H 9.29; found: C 62.9, H 9.1; H NMR (500 MHz, C
.14 (s, 9H; C-SiMe ), 1.96 (s, 6H; C-Me), 2.04 ppm (s, 6H; C-Me); C-
H} NMR (125 MHz, C , 258C): d=1.3 (C-SiMe ), 10.8 (C-Me), 14.0
C-Me), 77.7 (C-SiMe ), 122.6 (C-Me), 125.0 ppm (C-Me).
Me )(C Me SiMe )] (6) and [Zn(C Me
7): The mixed-ring zincocenes 6 and 7 were prepared by conproportio-
6
D
6
3
knowledged (FEDER support). I.R. thanks the Ministry of Education for
a research grant. D.d.R.J. thanks the sixth framework program of the
E.U. for a MC fellowship. A.R. and R.F. thank the MEC/Universidad de
Sevilla for a Ramꢄn y Cajal contract.
3
[
6
5
4
2
2
1
6 6
D , 258C):
d=0.14 (s, 6H; SiMe
2
(
(
2
2
1
3
1
6 6
D
2
3
3
[2] a) E. O. Fischer, W. Pfab, Z. Naturforsh. B 1952, 7, 377–379; b) G.
[
5
4
3 2
)
1
6
0
6 6
D , 258C): d=
1
3
3
1
{
6
D
6
3
[
Metallocenes, Vol. 1 (Eds: A. Togni , R. L. Halterman), Wiley-VCH,
Weinheim, 1998, Chapter 2; d) M. Bochmann in Comprehensive Or-
(
3
Synthesis of [Zn(C
(
5
5
5
4
3
5
5 5 4 3
)(C H SiMe )]
nation of [Zn(C
5
Me
5
)
2
] and the corresponding [ZnCp’
Me
and 5 (3.9, 8.6 mmol) were used to give the desired compound (3.5 g, ca.
0% isolated yield). The compound proved difficult to crystallise, but
suitable crystals were obtained from 1,4-dioxane. In the case of 7,
Zn(C Me ] (0.67 g, 2 mmol) and 1 (0.68 g, 2 mmol) were used to give a
2
] at 608C for 24 h,
with THF as the reaction solvent. For 6, [Zn(C
5
5 2
) ] (2.9 g, 8.6 mmol)
5
[
4] a) V. M. Rayꢄn, G. Frenking, Chem. Eur. J. 2002, 8, 4693–4707;
b) O. Kwon, M. L. McKee in Computational Organometallic
Chemistry (Ed.: T. R. Cundari), Marcel Dekker, New York, 2001,
[
5
5 2
)
yellow oil after removal of the solvent under vacuum. Washing the oil
with pentane at ꢀ508C afforded 0.9 g (66% yield) of 7.
[
5 5 5 4 3
Zn(C Me )(C Me SiMe )] (6): Elemental analysis calcd (%): C 67.07, H
[
1
9
9
6
(
1
.21; found: C 68.0, H 9.4; H NMR (500 MHz, C
H; SiMe ), 1.90 (s, 15H; CH -Cp*), 1.96 (s, 6H; CH
H; CH -Cp); C{ H } NMR (125 MHz, C , 258C): d=0.8 (SiMe
-Cp’), 11.3 (CH -Cp’), 15.2 (CH -Cp*), 51.4 (Cipso), 107.4 (C
30.3 (C -(C Me SiMe )), 130.4 ppm (C -(C Me SiMe )).
Me )(C SiMe )] (7): H NMR (500 MHz, C
s, 9H; SiMe ), 1.83 (s, 15H; CH -Cp*), 6.44 (s, 2H; CH), 6.87 ppm (s,
6
D
6
, 258C): d=0.06 (s,
-Cp), 2.03 ppm (s,
), 9.5
Me ),
3
3
3
1
3
1
3
6
D
6
3
CH
3
3
3
5
5
Walther, D. J. Berg, R. A. Andersen, Organometallics 2007, 26,
q
5
4
3
q
5
4
3
1
[
Zn(C
5
5
5
H
4
3
6 6
D , 258C): d=0.02
(
3
3
934
ꢉ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 924 – 935