H.J. Breunig et al. / Journal of Organometallic Chemistry 695 (2010) 1307–1313
1311
(SbC6H5-ortho), 167.34 (SbC6H5-ipso). MS (ESI, CH3CN), m/z (%),
49.82; H, 6.27. Found: C, 49.72; H, 6.78%. 1H NMR (300 MHz,
DMSO-d6): d 1.11 m (12H, NCH2CH3), 3.14q (8H, NCH2CH3, JHH
pos.: 130 (100) [Et4N+]; neg.: 417 (100) [Ph2SbCl4ꢀ].
3
7.2 Hz), 7.38 m (6H, SbC6H5-meta + para), 7.81 m (4H, SbC6H5-
4.5. Synthesis of [Bu4N]+[Ph2SbCl4]ꢀ (4)
ortho). 13C NMR (75.4 MHz, DMSO-d6):
d
6.90 (NCH2CH3),
51.30 m (NCH2CH3), 127.63 (SbC6H5-meta), 128.75 (SbC6H5-para),
3
2
To a solution of Bu4NClꢁH2O (0.89 g, 3.0 mmol) in 50 ml metha-
nol was added dropwise, under stirring, a solution of Ph2SbCl3ꢁH2O
(1.20 g, 3.0 mmol) in 50 ml methanol, at room temperature. The re-
sulted suspension was stirred for 1 h, then filtered and the solid
was washed with 5 ml methanol. The solid was dissolved in
20 ml acetonitrile and the solution, left in open atmosphere, depos-
ited within 24 h air stable, colorless crystals which were filtered
off. Yield: 1.94 g (98%). M.p. 169 °C. Anal. Calc. for C28H46Cl4NSb:
C, 50.94; H, 7.02. Found: C, 51.11; H, 6.96%. 1H NMR (200 MHz,
133.02qv (SbC6H5-ortho, JFC 2.0 Hz), 149.92 (SbC6H5-ipso, JFC
37.0 Hz). 19F NMR (282.4 MHz, DMSO-d6): d ꢀ103.2. MS (ESI,
CH3CN), m/z (%), pos.: 611 (30) [M+Et4N+], 130 (100) [Et4N+];
neg.: 351 (100) [Ph2SbF4ꢀ].
4.9. Synthesis of [Et4N]+[Ph2SbBr4]ꢀ (8)
A solution of Et4NBr (0.09 g, 0.44 mmol) in 15 ml acetonitrile
was added dropwise to a stirred solution of Ph2SbBr3 (0.23 g,
0.44 mmol) in 15 ml acetonitrile. After 24 h of stirring at room
temperature the solvent was removed in vacuum and a white pow-
der was isolated. The title compound was recrystallized from ace-
tonitrile to give a colorless microcrystalline product. Yield: 0.25 g
(88%). M.p. 245–247 °C. 1H NMR (200 MHz, DMSO-d6): d 1.15 m
3
CDCl3): d 0.85t [12H, NCH2(CH2)2CH3, JHH 7.0 Hz], 1.89 m [16H,
3
NCH2(CH2)2CH3], 2.84t [8H, NCH2(CH2)2CH3, JHH 8.0 Hz], 7.32 m
3
(6H, SbC6H5-meta + para), 8.39d (4H, SbC6H5-ortho, JHH 8.0 Hz).
13C NMR (50.3 MHz, DMSO-d6): d 13.60 (Cd), 19.51 (C ), 23.82
c
(Cb), 58.57 (C ), 127.44 (SbC6H5-meta), 128.75 (SbC6H5-para),
a
3
131.04 (SbC6H5-ortho), 167.89 (SbC6H5-ipso). MS (ESI, CH3CN), m/
(12H, NCH2CH3), 3.20q (8H, NCH2CH3, JHH 7.3 Hz), 7.45 m (6H,
z (%), pos.: 242 (100) [Bu4N+]; neg.: 417 (100) [Ph2SbCl4ꢀ].
SbC6H5-meta + para), 8.06d (4H, SbC6H5-ortho, JHH 7.4 Hz). 13C
3
NMR (50.3 MHz, DMSO-d6): d 7.02 (NCH2CH3), 51.29 m (NCH2CH3),
128.10 (SbC6H5-meta), 129.28 (SbC6H5-para), 129.85 (SbC6H5-
ortho), 161.59 (SbC6H5-ipso). MS (ESI, CH3CN), m/z (%), pos.: 130
(100) [Et4N+]; neg.: 595 (100) [Ph2SbBr4ꢀ].
4.6. Synthesis of [Me4Sb]+[Ph2SbCl4]ꢀ (5)
A suspension of Me4SbI (1.43 g, 4.6 mmol) in 30 ml methanol
was added dropwise to
a
solution of Ph2SbCl3ꢁH2O (1.85 g,
4.6 mmol) in 50 ml of a 1:1 mixture of HCl (37% in water) and
methanol and the mixture was stirred for 2 h. The color changed
from yellow to brown and a white solid precipitated. The solid
was filtered off and then solved in CH3CN. The solution, left in
the open atmosphere at room temperature, deposited air stable,
colorless crystals of 5. Yield: 1.85 g (72%). M.p. 247 °C. Anal. Calc.
for C16H22Cl4Sb2: C, 32.05; H, 3.70. Found: C, 32.26; H, 4.33%. 1H
NMR (200 MHz, DMSO-d6): d 1.49s (12H, SbCH3), 7.39 m (6H,
4.10. Reaction of Et4NBr and Ph2SbCl3ꢁH2O
A solution of Et4NBr (0.17 g, 0.82 mmol) in 20 ml methanol was
added dropwise to a solution of Ph2SbCl3ꢁH2O (0.33 g, 0.82 mmol)
in 20 ml methanol, under stirring, at room temperature. After
24 h the solvent was removed in vacuum and a white powder
was obtained. The product was recrystallized from acetonitrile to
give colorless crystals (0.27 g, 56%). Anal. Calc. for C20H30BrCl3NSb:
C, 40.54; H, 5.10. Found: C, 40.38; H, 5.82%. MS (ESI, CH3CN), m/z
(%), pos.: 130 (100) [Et4N+]; neg.: 595 (80) [Ph2SbBr4ꢀ], 550 (100)
[Ph2SbBr3Clꢀ], 506 (24) [Ph2SbBr2Cl2ꢀ], 461 (2) [Ph2SbBrCl3ꢀ].
3
SbC6H5-meta + para), 8.21d (4H, SbC6H5-ortho, JHH 7.2 Hz). 13C
NMR (50.3 MHz, DMSO-d6): d 2.23 (SbCH3), 127.37 (SbC6H5-meta),
128.86 (SbC6H5-para), 130.42 (SbC6H5-ortho), 167.34 (SbC6H5-ipso).
MS (ESI, CH3CN), m/z (%), pos.: 181 (100) [Me4Sb+]; neg.: 417 (100)
[Ph2SbCl4ꢀ].
4.11. Reaction of Ph4PBr and Ph2SbCl3ꢁH2O
4.7. Synthesis of [Et3MeSb]+[Ph2SbCl4]ꢀ (6)
A solution of Ph4PBr (2.2 g, 5.2 mmol) in 30 ml methanol was
added dropwise to a solution of Ph2SbCl3ꢁH2O (2.0 g, 5.0 mmol)
in 50 ml methanol, under stirring, at room temperature. The reac-
tion mixture was stirred for 2 h, then the white solid formed was
filtered off and solved in acetonitrile. Exposure of the solution to
the open atmosphere gave white crystals (1.61 g, 41%). MS
(ESI, CH3CN), m/z (%), pos.: 339 (100) [Ph4P+]; neg.: 506 (8)
[Ph2SbBr2Cl2ꢀ], 461 (32) [Ph2SbBrCl3ꢀ], 417 (100) [Ph2SbCl4ꢀ].
A solution of Et3MeSbI (0.87 g, 2.5 mmol) in 10 ml methanol
was added dropwise to Ph2SbCl3ꢁH2O (1.0 g, 2.5 mmol) in 15 ml
of methanol and the mixture was stirred for 1 h. The color changed
from yellow to dark brown and a light yellow precipitate formed.
The solid was filtered off and then solved in CH3CN. Slow evapora-
tion of the solvent in the open atmosphere gave colorless crystals
of 6. Yield: 0.8 g (43%). M.p. 152 °C. 1H NMR (200 MHz, DMSO-
3
d6): d 1.30t (9H, SbCH2CH3, JHH 7.9 Hz), 1.38s (3H, SbCH3), 2.17q
4.12. Reaction of Ph4SbBr and Me2SbCl3
3
(6H, SbCH2CH3, JHH 7.9 Hz), 7.41 m (6H, SbC6H5-meta + para),
8.22 m (4H, SbC6H5-ortho). 13C NMR (50.3 MHz, DMSO-d6): d
ꢀ4.63 (SbCH3), 9.09 (SbCH2CH3), 11.83 (SbCH2CH3), 127.34
(SbC6H5-meta), 128.83 (SbC6H5-para), 130.39 (SbC6H5-ortho),
167.32 (SbC6H5-ipso). MS (ESI, CH3CN), m/z (%), pos.: 223 (100) [Et3-
MeSb+]; neg.: 417 (100) [Ph2SbCl4ꢀ].
A solution of Ph4SbBr (0.4 g, 0.7 mmol) in 25 ml methanol was
added dropwise to Me2SbCl3 (0.2 g, 0.7 mmol) in 30 ml methanol.
The mixture was stirred for 1 h at room temperature and the sol-
vent was removed in vacuum. The remaining solid was solved in
acetonitrile and the solution was exposed to the atmosphere to
produce white crystals which were separated by filtration
(0.52 g, 37%).
4.8. Synthesis of [Et4N]+[Ph2SbF4]ꢀ (7)
A solution of NaF (0.3 g, 7.1 mmol) in 20 ml acetonitrile was
added dropwise to a stirred solution of [Et4N]+[Ph2SbCl4]ꢀ (3)
(0.5 g, 0.9 mmol) in 20 ml acetonitrile at room temperature. After
24 h of stirring the solvent was removed in vacuum and a white
powder was isolated. The title compound was recrystallized from
acetonitrile to give a colorless microcrystalline product. Yield:
0.34 g (78%). M.p. 151–153 °C. Anal. Calc. for C20H30F4NSb: C,
4.13. Reaction of Ph4SbBr and Ph2SbCl3
A solution of Ph4SbBr (0.5 g, 0.9 mmol) in 20 ml methanol was
added dropwise to Ph2SbCl3 (0.37 g, 0.9 mmol) in 30 ml methanol.
The mixture was stirred for 1 h at room temperature and the sol-
vent was removed in vacuum. The remaining solid was solved in
acetonitrile and the solution was exposed to the atmosphere to