2
K.R. Cairns et al. / Journal of Organometallic Chemistry 912 (2020) 121176
1
2
. Experimental
3JHH ¼ 8 Hz, CH
3
). 13C{ H} NMR (CH
2
Cl
2
, 295 K):
d
¼ 28.6 (CH
2
), 26.4
/CD Cl , 293 K):
71
(CH
2
), 14.9 (CH
2
), 13.7 (CH
3
). Ga NMR (CH
2
Cl
2
2
2
ꢀ
1
Infrared spectra were recorded as Nujol mulls between CsI
d
¼ 115.9. IR (Nujol): v ¼ 276, 221 cm GaeBr.
plates using a PerkinElmer 100 spectrometer over the range 4000ꢀ
ꢀ
1 1
13
1
31
1
n
2
00 cm . H (400 Mhz), C{ H} (100.6 Mhz), P{ H} (161.9 MHz),
2.4. [GaI
3
(Sb Bu
3
)]
7
1
115
Ga (122.0 MHz), and In (87.6 MHz) NMR spectra were recorded
from CH
2
Cl
2
/CD
2
Cl
2
, solutions using a Bruker AV400 spectrometer
GaI
3
(0.428 g, 1.07 mmol) was suspended in n-hexane (10 mL)
and referenced to TMS via the residual solvent resonance, 85%
before a solution of tributylstibine (0.315 g, 1.07 mmol) in n-hexane
(3 mL) was added. The yellow suspension was left to stir for 3 h,
before the solvent was removed by filtration, to afford a pale-yellow
3
þ
3þ
6
H
3
PO
4
, [Ga(H
2
O)
6
]
and [In(H
2
O)
]
2 2
in H O/D O at pH 1,
respectively. Microanalyses were undertaken at London Metro-
politan University. Hexane and diethyl ether were dried by distil-
solid which was dried in vacuo. Yield 0. 610 g, 77%. Anal. Calcd for
1
lation from sodium and CH
2
Cl
2
from CaH
2
, and all preparations
C
12
H I
27 3
GaSb (743.5): C, 19.40; H, 3.66. Found: C, 19.20; H, 3.74%. H
were carried out under rigorously anhydrous conditions via a dry
dinitrogen atmosphere and standard Schlenk and glovebox tech-
NMR (CD
2
Cl
2
, 293 K):
(m, [2H], JHH ¼ 8 Hz, CH
293 K): ), 26.6 (CH
(CH Cl , 293 K):
¼ 236.4. IR (Nujol): v ¼ 230, 209 cm
GaeI.
d
¼ 2.11 (t, [2H], CH
), 0.96 (t, [3H], CH
), 15.2 (CH
2
), 1.77 (m, [2H], CH
2
), 1.45
). C{ H} NMR (CD Cl
2 3
), 13.7 (CH ). Ga NMR
3
13
1
2
3
2
2
,
71
niques. GaCl
GaBr from Alfa Aesar, GaI
used as received. The complexes of SbEt
7].
Caution! Some trialkylstibines are pyrophoric, and care should
3
, InCl
3
, and InBr
from Strem, and InI
were made as described
3
were purchased from Sigma-Aldrich,
d
¼ 28.4 (CH
2
2
ꢀ1
3
3
3
from Fisher; and
2
2
/CD
2
Cl
2
d
3
[
n
2.5. [InCl
3
(Sb Bu
3
)]
be taken to manipulate them under strictly anaerobic conditions.
InCl
before a solution of tributylstibine (0.630 g, 2.16 mmol) in n-hexane
3 mL) was added. The white suspension was left to stir for 3 h,
before the volatiles were removed in vacuo. The product was
extracted in CH Cl (3 mL) and the solvent removed in vacuo to
3
(0.478 g, 2.16 mmol) was dissolved in n-hexane (10 mL)
n
2
.1. Sb Bu
3
(
Magnesium turnings (8.5 g, 349 mmol) were stirred under ni-
trogen overnight. Diethyl ether (~200 mL) was added, and the
stirring suspension was placed into an ice bath before a mixture of
BuBr (36.3 g, 265 mmol) with diethyl ether (30 mL) was added
dropwise. The suspension turned black and was left to stir over-
2
2
afford
a
white solid. Yield 0.489 g, 44%. Anal. Calcd for
n
C
12
H
27Cl
3
InSb (514.3): C, 28.03; H, 5.29. Found: C, 28.15; H, 5.33%.
1
3
H NMR: (CD
2
Cl
[2H], JHH ¼ 8 Hz, CH
1
2
, 293 K):
d
¼ 2.20 (t, [2H], JHH ¼ 8 Hz, CH
2
),1.75 (m,
), 0.96 (t, [3H],
¼ 29.2 (CH ), 26.5
/CD Cl , 293 K): Not
ꢁ
3
3
night at room temperature. The mixture was cooled to 0 C and an
2
), 1.44 (m, [2H], JHH ¼ 8 Hz, CH
2
3
13
ethereal solution of SbCl
A grey precipitate formed, and the mixture was then refluxed for
0 min. The mixture was cooled, hydrolysed with degassed water,
and the organic layer was separated and dried with degassed
magnesium sulphate before the solution was filtered and trans-
ferred to a Schlenk flask were the remaining ether was removed in
vacuo, leaving a yellow oil. This was distilled at 85 C/1 mm Hg,
producing a colourless oil. Yield 13.0 g, 64%. H NMR (CD
93 K):
.91 (t, [3H],
¼ 30.6 (CH
3
(12.05 g, 53 mmol) was added dropwise.
J
HH ¼ 8 Hz, CH
3
). C{ H} NMR (CD
2
Cl2, 295 K):
d
2
1
15
(CH ), 15.6 (CH
observed. IR (Nujol): v ¼ 336, 310, cm In-Cl.
2
2
), 13.7 (CH
3
). In NMR (CH Cl
2
2
2
2
ꢀ
1
9
n
2.6. [InBr
3
(Sb Bu
3
)]
ꢁ
InBr
3
(0.381 g, 1.07 mmol) was dissolved in n-hexane (10 mL)
1
2
Cl
2
,
),
before a solution of tributylstibine (0.315 g, 1.07 mmol) in n-hexane
(3 mL) was added. The white suspension was left to stir for 3 h,
before the solid was filtered off to afford an off-white solid which
3
2
0
d
d
¼ 1.52 (t, [2H], JHH ¼ 8 Hz
,
CH
2
), 1.45e1.33 (m, [4H], CH
2
3
13
1
J
HH ¼ 8 Hz, CH
3
). C{ H} NMR (CD
Cl , 293 K):
2 2
2
), 27.0 (CH
2
), 14.8 (CH ), 14.1 (CH ).
2
3
was dried in vacuo. Yield 0.524 g, 76%. Anal. Calcd for C12
H
27Br
3
InSb
1
(
647.6): C, 22.25; H, 4.40. Found: C, 22.09; H, 4.07%. H NMR
n
3
2
.2. [GaCl
3
(Sb Bu
3
)]
(CD
2
Cl
2
, 293 K):
d
¼ 2.19 (t, [2H], JHH ¼ 8 Hz, CH
2
), 1.75 (m, [2H],
), 0.96 (t, [3H],
¼ 29.1 (CH ), 26.5
/CD Cl , 293 K):
3
3
J
J
HH ¼ 8 Hz, CH
2
), 1.44 (m, [2H], JHH ¼ 8 Hz, CH
2
3
13
1
GaCl
before a solution of tributylstibine (0.473 g, 1.60 mmol) in CH
3 mL) was added. The pale-yellow suspension was stirred for 3 h
before the solvent was filtered off to afford a pale-yellow waxy
solid, which was dried in vacuo. Yield 0.653 g, 88%. Anal. Calcd for
3
(0.285 g, 1.60 mmol) was suspended in CH
2
Cl
2
(10 mL)
HH ¼ 8 Hz, CH
3
). C{ H} NMR (CD
2
Cl
2
, 293 K):
d
2
115
2
Cl
2
(CH
2
), 15.7 (CH
2
), 13.7 (CH
3
).
In NMR (CH
2
Cl
2
2
2
ꢀ
1
(
d
¼ 278.2 (broad). IR (Nujol): v ¼ 214, 211 cm In-Br.
n
2.7. [InI
3
(Sb Bu
3
)]
12 3
C H27Cl GaSb (469.2): C, 30.70; H, 5.80. Found: C, 30.90; H, 5.72%.
1
3
H NMR (CD
2H], CH
), 1.41 (m, [2H], JHH ¼ 8 Hz, CH
H} NMR (CD Cl , 293 K):
¼ 29.1 (CH
). Ga NMR (CH Cl /CD Cl , 293 K):
2
Cl
2
, 293 K):
d
¼ 1.98 (t, [2H], JHH ¼ 8 Hz, CH
2
): 1.67 (m,
InI
3
(0.530 g, 1.07 mmol) was suspended in n-hexane (10 mL)
3
13
[
{
2
2
), 0.94 (t, [3H], CH
3
).
C
),
before a solution of tributylstibine (0.315 g, 1.07 mmol) in n-hexane
(3 mL) was added. The pale-yellow suspension was left to stir for
3 h, before the mixture was filtered to afford a pale-yellow solid
1
2
2
d
2
), 26.5 (CH ), 14.7 (CH
2
2
71
1
3.7 (CH
3
2
2
2
2
d
¼ 252.5. IR (Nujol):
ꢀ1
v ¼ 377, 347 cm GaeCl.
which was dried in vacuo. Yield 0.670 g, 79%. Anal. Calcd for
1
C
12
H
27
I
3
InSb (788.6): C, 18.26; H, 3.45. Found: C, 18.09; H, 3.52%. H
n
2
.3. [GaBr
3
(Sb Bu
3
)]
NMR (CD
2
Cl
2
, 293 K):
m, [2H], JHH ¼ 8 Hz, CH
NMR (CD Cl , 293 K):
¼ 28.2 (CH
). In NMR (CH Cl /CD Cl , 293 K): d
d
¼ 2.26 (t, [2H], CH
2
),1.78 (m, [2H], CH
2
),1.45
3
3
13
1
(
2
), 0.97 (t, [3H], JHH ¼ 8 Hz, CH
), 26.5 (CH
¼ ꢀ235 (broad).
3
). C{ H}
GaBr
before a solution of tributylstibine (0.316 g, 1.07 mmol) in n-hexane
3 mL) was added. The pale-yellow suspension was left to stir for
h, before the volatiles were removed under vacuum. The product
then extracted with CH Cl before drying in vacuo to afford a pale-
yellow solid, which later degraded into an oil. Yield 0.460 g, 71%. H
3
(0.333 g, 1.08 mmol) was suspended in n-hexane (10 mL)
2
2
d
2
2 2
), 17.5 (CH ), 13.8
1
15
(CH
3
2
2
2
2
(
3
3 3 2
2.8. [InCl (PEt ) ]
2
2
1
InCl
before dropwise addition of PEt
mixture stirred for 3 h. The solvent was removed, leaving a white
3
(0.055 g, 0.250 mmol) was suspended in CH
2 2
Cl (15 mL)
3
NMR (CD
2
Cl
2
, 293 K):
d
¼ 2.12 (t, [2H], JHH ¼ 8 Hz, CH
2
), 1.74 (m,
3
(0.060 g, 0.500 mmol) and the
3
3
[2H], JHH ¼ 8 Hz, CH
2
), 1.44 (m, [2H], JHH ¼ 8 Hz, CH
2
), 0.95 (t, [3H],