U. Radius et al. / Journal of Organometallic Chemistry 655 (2002) 96ꢁ
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103
1
3.10. Synthesis of [Cp*Mo(Nt-Bu)(m-Nt-Bu)]2 (7)
material, m.p. 157 8C. H-NMR (400 MHz, C6H6-d6):
2.09 (s, 9H), 2.34 (s, 18H), 6.65 (s, 6H) ppm. 13C-NMR
(100 MHz, C6H6-d6): 153.6, 136.9, 132.4, 128.4, 20.9,
18.7 ppm. IR (Nujol): 1605 m, 1466 vs, br, 1378 s, 1317
m, 1287 vs, 1260 vw, 1162 vw, 1032 w, br, 989 m, 853 s,
C8K (150 mg, 1.11 mmol) are added to a solution of
300 mg (0.73 mmol) [Cp*Mo(Nt-Bu)2Cl] in 40 ml
toluene and the suspension is treated with ultrasound
for 90 min. Insoluble parts are separated by filtration via
celite. Volatiles of the filtrate are completely removed in
798 w, 730 m, 720 s, 597 w, 593 w, 392 w, 361 s cmꢃ1
EIMS: m/zꢀ NMes,
621.1 ([M]ꢂ, 29%), 487.2 ([M]ꢂ Ã
16%), 135.1 (MesNH2, 100%). Anal. Found: C, 52.44;
H, 5.72; N, 6.56. Calc. for C27H33ClN3Re (621.2): C,
52.21; H, 5.35; N 6.76%.
.
/
/
vacuo and the orangeꢁ
/
brown residue is crystallized
from n-pentane at ꢃ80 8C. Yield: 102 mg (82%) orange
/
1
crystals, m.p. 103 8C. H-NMR (200 MHz, C6H6-d6),
only one isomer detectable: 1.11 (s, 9H), 1.90 (s, 9H),
1.98 (s, 15H). 13C-NMR (50 MHz, C6H6-d6): 14.4, 33.2,
33.9, 66.3, 69.3, 114.3 ppm. IR (Nujol): 1208 vs and
3.13. Synthesis of [Re(NMes)2(m-NMes)]2 (10)
[Re(NMes)3Cl] (250 mg, 0.402 mmol) are dissolved in
1176 s n(MoÄ
w, 752 vw, 720 w, 685 vw, 620 sh, 556 w, 516 m, 492 w,
460 w, 424 w cmꢃ1. EIMS: m/zꢀ746 ([M]ꢂ, 13%), 611
C10H15, 85%), 134 ([C10H15]ꢂ, 44%), 119
/
NÃ/C), 1112 m, 1020 m, 968 m, 912 w, 804
10 ml THF. At ꢃ80 8C 0.44 ml (0.443 mmol) of 1.0 M
/
/
[LiBEt3H] in THF. Within 1 h the solution is warmed
upto r.t. where it is kept there for 1 h. The product
separates as an orange precipitate. Precipitation is
completed at 0 8C, the solids are filtered into a frite
and extracted from the frite into with 20 ml toluene. All
volatiles are removed in vacuo and the residue is
crystallized from hot THF. Yield: 375 mg (80%) red
([M]ꢂ Ã
/
([C9H11]ꢂ, 100%). Anal. Found: C, 58.21; H, 9.23; N,
7.80. Calc. for C36H66Mo2N4 (746.8): C, 57.90; H, 8.91;
N, 7.50%.
3.11. Synthesis of [Re(NMes)3OSiMe3] (8)
1
crystals, m.p. 245 8C. H-NMR (400 MHz, CHCl3-d):
Re2O7 (500 mg, 1.03 mmol) are dissolved in 20 ml
(94.1 mmol) (Me3Si)2O at 40 8C. To this solution 1.40 g
(12.9 mmol) Me3SiCl, 1.31 g (12.9 mmol) NEt3 and
0.837 g (6.19 mmol) MesNH2 are added and the mixture
is stirred for 26 h at 45 8C. The soluble parts are
separated by filtration via Celite and the solvent was
stripped in vacuo. The red oily residue is dissolved with
1.93 (s, 12H), 1.99 (s, 24H), 2.19 (s, 12H), 2.33 (s, 6H),
6.70 (s, 8H), 6.88 (s, 4H) ppm. 13C-NMR (100 MHz,
CHCl3-d): 18.8, 19.3, 20.9, 22.6, 127.9, 129.3, 132.2,
133.5, 133.9, 135.4, 153.1, 157.3 ppm. IR (Nujol): 1606
m n(CÄ
n(ReÄNÃ
m, 885 s, 803 w, br, 726 m, 602 w cmꢃ1. EIMS: m/zꢀ
NMes, 31%). Anal.
/
C), 1377 m, 1341 vs, 1320 vs, 1290 s and 1227 m
/
/
C), 1163 w, 1096 vw, br, 1028 w, 1015 w, 991
/
5ꢁ
/
10 ml pentane. At ꢃ30 8C product crystallizes.
/
1171 ([M]ꢂ, 36%), 1039 ([M]ꢂ Ã
/
Yield: 225 mg (32%), orangeꢁred solid, m.p. 45 8C
/
Found: C, 53.75; H, 5.58; N, 6.65. Calc. for
C54H66N6Re2 (1171.6): C, 55.36; H, 5.68; N, 7.17%.
(dec.). 1H-NMR (400 MHz, C6H6-d6): 0.34 (s, 9H), 2.12
(s, 9H), 2.38 (s, 18H), 6.72 (s, 6H) ppm. 13C-NMR (100
MHz, C6H6-d6): dꢀ153.5, 134.9, 131.7, 128.4, 20.9,
/
18.7, 2.03 ppm. IR (Nujol): 1605 w, 1463 vs, br, 1377 s,
1326 s, 1290 s, 1260 vw, 1249 m, 1163 w, 1013 w, 988 w,
888 s, br, 849 s, 837 m, 796 vw, 748 w, 720 m, 388 w
cmꢃ1. Anal. Found: C, 53.71; H 6.14; N 6.15. Calc. for
C30H42N3OReSi (675.0): C, 53.39; H, 6.27; N, 6.23%.
3.14. Crystal structure determination of 10
Single crystals were obtained from THF. Compound
10 crystallizes in the monoclinic space group P21/n (No.
˚
11) with aꢀ
aꢀgꢀ908, bꢀ
crystal with the dimensions 0.3ꢄ
used. Intensity data were measured at 213 K with a
EnrafꢁNonius CAD4 (MoꢁKa radiation, lꢀ0.70930
A) upto Tmax 298, yielding 7849 unique reflections, of
/
14.655(1), bꢀ
/
9.776(1), cꢀ
/
21.097(3) A,
3
˚
/
/
/
105.978(7)8, Vꢀ
/
2905.7(4) A , Zꢀ
/
4. A
3.12. Synthesis of [Re(NMes)3Cl] (9)
/
0.2ꢄ
0.1 mm3 was
/
To a suspension of 5 g (10.3 mmol) Re2O7 in 200 ml
CH2Cl2 at 0 8C are added successively 8.37 g (61.9
mmol) MesNH2, 14.6 g (144.5 mmol) NEt3 and 17.9 g
(165.2 mmol) Me3SiCl. The reaction mixture is stirred at
25 8C for 3 days. After all volatiles have been removed,
the residue is extracted into toluene, insoluble material is
separated by filtration, toluene is completely removed in
vacuo and the dark red solid still containing NMR
/
/
/
˚
ꢀ
/
which 6011 were observed. The absorption coefficient
was 4.209 mmꢃ1, no absorption correction. The struc-
ture was solved by direct methods (SHELXS-86 and
SHELXS-97) [36] and refined [37] by least-squares meth-
ods based on F2 with all reflections to Rꢀ
wR2ꢀ0.1267; residual electron density located at the
2.921 e Aꢃ3. Non-hydrogen
˚
rhenium atom 2.291/ꢃ
/
0.0454 and
/
signals which are attributed to a [ReÃ
/
OSiMe3] group is
/
again stirred with 8 ml Me3SiCl at r.t. for 24 h. Finally
removal of all volatiles at 10ꢃ3 mbar leads to a dark red
atoms were refined anisotropically, hydrogen atoms
were inserted in calculated positions. The asymmetric
unit contains one molecule THF and one molecule of
the complex.
solid, which is suspended and washed at ꢃ
/
30 8C with
pentane. Yield: 3.51 g (53%), dark red crystalline