4782 Inorganic Chemistry, Vol. 38, No. 21, 1999
Narula et al.
2
13
3
13
5
71/546 Hz), 25.5 (C
2
, J( C-119Sn) ) 26 Hz), 26.3 (C
3
, J( C-
3
195.5 (CO), 98.1 (CH), 26.6 (dik CH ), 136.2, 132.8, 128.6, 127.7 (Ph).
Sn{ H} NMR (149.21 MHz, CDCl ): δ -246.3. IR (Nujol, cm ):
3
119
119
1
119
1
-1
Sn) ) 80 Hz). Sn{ H} NMR (149.21 MHz, CDCl
IR (Nujol, cm ): 1275, 1150, 1080 (ν(SO
SSn: C, 33.45; H, 6.73; S, 8.93; Sn, 33.06. Found: C, 33.17; H, 6.70;
S, 8.70; Sn, 33.22.
3
): δ -178.9.
)). Anal. Calcd for C10
-1
3
H
24
4
O -
1260, 1140, 1060 (ν(SO
m/z 433 [M - Bu] , 395 [M - OSO
3
)), 1520 (ν(CO)). Mass spectrum (EI, 70 eV):
+
+
+
2
Me] , 281 [Sn(bzac)] . Anal.
Calcd for C19
C, 46.47; H, 6.11; S, 6.41; Sn, 23.90.
n-Pr Sn(bzbz)OS(O) Me (9). This compound was prepared from
30 5
H O SSn: C, 46.64; H, 6.18; S, 6.55; Sn, 24.26. Found:
(C
6
H
11
)
2
Sn(OMe)OS(O)
white solid. Yield: 1.25 g, 58.4%. H NMR (300 MHz, CDCl
.85 (s, 3H, SCH ), 3.55 (s, 3H, OCH ), 2.05 (m, 8H, ring H), 1.65
m, 14H, ring H). C{ H} NMR (100.61 MHz, CDCl ): δ 55.3
OCH ), 39.5 (SCH ), 26.4, 28.6, 30.3, 45.5 (c-Hx carbons). Sn-
H} NMR (149.21 MHz, CDCl
140, 1070 (ν(SO )). Anal. Calcd for C14
2
Me (4). This compound was isolated as a
1
3
): δ
2
2
2
3
3
1 (0.64 g, 1.94 mmol) and dibenzoylmethane (0.43 g, 1.94 mmol) by
a procedure analogous to that used to synthesize 5. Compound 9 was
1
3
1
(
(
{
3
1
19
1
3
3
isolated as a pale yellow solid. Yield: 0.78 g, 77.1%. H NMR (300
1
-1
3
): δ -262.7. IR (Nujol, cm ): 1250,
SSn: C, 40.89; H, 6.86;
MHz, CDCl
(t, 6H, CH
(100.61 MHz, CDCl
618/592 Hz), 17.2 (C
3
3 2 2
): δ 2.90 (s, 3H, SCH ), 1.81 (m, 8H, SnCH CH ), 1.01
13
1
1
3
H O
28 4
3
), 6.85 (s, 1H, CH), 7.40-8.20 (m, 10H, Ph). C{ H} NMR
1 13
119/117
3
S, 7.79; Sn, 28.87. Found: C, 40.66; H, 6.82; S, 7.57; Sn, 28.38.
3
): δ 39.7 (SCH
3
), 28.5 (C
1
, J( C-
Sn) )
2
13
119
13
Preparation of (â-Diketonato)diorganotin Methanesulfonates (5-
2
, J( C- Sn) ) 32 Hz), 17.3 (C
3
, J( C-
119
1
1). n-Pr
2
Sn(acac)OS(O)
2
Me (5). To a solution of methoxydi-n-
Sn) ) 96 Hz), 187.2 (CO), 95.0 (CH), 133.1, 128.7, 127.9 127.1
119 1
propyltin methanesulfonate (1) (0.70 g, 2.11 mmol) in dichloromethane
was added acetylacetone (0.21 g, 0.22 mL, 2.11 mmol), and the clear
solution was stirred for 4-5 h at room temperature. The solvent was
removed under vacuo, and n-hexane was added. The white solid thus
obtained was filtered off, washed with n-hexane, and dried under
vacuum. Recrystallization of the product from a CH
mixture afforded 5 as a white solid. Yield: 0.67 g, 79.4%. H NMR
300 MHz, CDCl ): δ 2.90 (s, 3H, SCH ), 1.80 (m, 8H, SnCH CH ),
.02 (t, 6H, CH ), 2.17 (s, 6H, CH
NMR (100.61 MHz, CDCl
(Ph). Sn{ H} NMR (149.21 MHz, CDCl
3
): δ -270.6. IR (Nujol,
-
1
cm ): 1260, 1135, 1055 (ν(SO
3
)), 1515 (ν(CO)). Mass spectrum (EI,
+
+
+
70 eV): m/z 481 [M - Pr] , 429 [M - OSO
2
Me] , 343 [Sn(bzbz)] ,
SSn: C, 50.50; H, 5.39;
+
215 [SnOSO
2
Me] . Anal. Calcd for C22
H
28
O
5
S, 6.12; Sn, 22.68. Found: C, 50.38; H, 5.41; S, 6.18; Sn, 22.81.
n-Bu Sn(bzbz)OS(O) Me (10). The reaction between methoxydi-
n-butyltin methanesulfonate (2) (0.70 g, 1.94 mmol) and dibenzoyl-
methane (0.43 g, 1.94 mmol) was conducted in CH Cl under the same
conditions as described for 5. Compound 10 was obtained as a pale
2
Cl
2
/n-hexane
2
2
1
(
1
3
3
2
2
2
2
13
1
3
3
CO), 5.85 (s, 1H, CH). C{ H}
1
13
119/117
1
3
2
): δ 39.6 (SCH
3
), 29.5 (C
1
, J( C-
Sn)
yellow solid. Yield: 0.89 g, 82.8%. H NMR (300 MHz, CDCl
2.91 (s, 3H, SCH ), 1.78 (m, 8H, SnCH CH ), 1.40 (m, 4H, CH ), 1.0
(t, 6H, CH
(100.61 MHz, CDCl
610/585 Hz), 26.6 (C
3
): δ
13
119
3
13
)
626/600 Hz), 18.1 (C
2
, J( C- Sn) ) 36 Hz), 17.7 (C
3
, J( C-
3
2
2
2
119
119
13
1
Sn) ) 103 Hz), 194.6 (CO), 101.9 (dCH), 27.6 (dik CH
3
-1
). Sn-
3
), 6.80 (s, 1H, CH), 7.45-8.20 (m, 10H, Ph). C{ H} NMR
1 13
{1
1
3
for C12
3
H} NMR (149.21 MHz, CDCl
)), 1520 (ν(CO)). Mass spectrum (EI, 70 eV): m/z
): δ -242.1. IR (Nujol, cm ): 1250,
119/117
3 1
): δ 39.7 (SCH ), 27.0 (C , J( C-
3
Sn) )
3
3
2
13
119
13
160, 1060 (ν(SO
3
2
, J( C- Sn) ) 32 Hz), 26.3 (C
Sn) ) 97 Hz), 13.5 (C
3
, J( C-
+
+
+
119
57 [M - Pr] , 305 [M - OSO
SSn: C, 36.11; H, 6.06; S, 8.03; Sn, 29.74. Found: C,
6.18; H, 5.94; S, 7.82; Sn, 29.66.
n-Bu Sn(acac)OS(O) Me (6). This compound was obtained as a
2
Me] , 219 [Sn(acac)] . Anal. Calcd
4
), 187.2 (CO), 95.0 (CH), 133.1, 128.7, 127.9,
119
1
H O
24 5
127.1 (Ph). Sn{ H} NMR (149.21 MHz, CDCl
3
): δ -274.0. IR
(Nujol, cm-1): 1280, 1130, 1050 (ν(SO
)), 1510 (ν(CO)). Mass
3
+
+
2
2
spectrum (EI, 70 eV): m/z 495 [M - Bu] , 438 [M - 2Bu] , 343
[Sn(bzbz)] , 215 [SnOSO Me] . Anal. Calcd for C24H O SSn: C,
2 32 5
+
+
white solid according to the procedure described for 5 by reacting
methoxydi-n-butyltin methanesulfonate, 2 (0.70 g, 1.94 mmol), with
acetylacetone (0.19 g, 0.20 mL, 1.94 mmol). Yield: 0.70 g, 84.3%. H
52.28; H, 5.85; S, 5.81; Sn, 21.53. Found: C, 52.07; H, 5.76; S, 5.66;
Sn, 20.81.
1
NMR (300 MHz, CDCl
3
): δ 2.87 (s, 3H, SCH
), 0.92 (t, 6H, CH ), 2.08 (s, 6H, CH
.70 (s, 1H, CH). C{ H} NMR (100.61 MHz, CDCl ): δ 39.4 (SCH
3
), 1.74 (m, 8H, SnCH
CO),
),
, J( C- Sn) )
2
-
2 2
i-Bu Sn(bzbz)OS(O) Me (11). This compound was isolated as a
pale yellow solid from the reaction of 3 (0.70 g, 1.94 mmol) and
CH ), 1.38 (m, 4H, CH
2
2
3
3
1
3
1
5
2
3
3
3
dibenzoylmethane (0.43 g, 1.94 mmol) by following a procedure similar
1
13
119/117
2
13
119
1
7.5 (C
1
, J( C-
Sn) ) 621/595 Hz), 26.3 (C
2
to that described for 5. Yield: 0.79 g, 73.5%. H NMR (300 MHz,
3
13
119
119
1
4 Hz), 28.8 (C
3
, J( C- Sn) ) 98 Hz), 13.3 (C
4
). Sn{ H} NMR
3
CCl ): δ 2.95 (s, 3H, SCH
3 2
), 2.20 (m, 2H, CH), 1.70 (d, 4H, SnCH ),
-1
(
149.21 MHz, CDCl
)), 1535 (ν(CO)). Mass spectrum (EI, 70 eV): m/z 371 [M -
Bu] , 333 [M - OSO
3
): δ -239.3. IR (Nujol, cm ): 1260, 1155, 1060
1.05 (d, 12H, CH
3
), 6.80 (s, 1H, â-dik CH), 7.50-8.15 (m, 10H, Ph).
1
3
1
1
13
(ν(SO
3
C{ H} NMR (100.61 MHz, CDCl
3
): δ 39.7 (SCH
3
), 37.0 (C
, J( C- Sn) ) 27 Hz), 26.0 (C
J( C- Sn) ) 82 Hz), 186.9 (CO), 95.0 (dik CH), 133.1, 128.8, 128.0,
1
, J( C-
+
+
+
119/117
2
13
119
2
Me] , 219 [Sn(acac)] . Anal. Calcd for C14
28
H O
5
-
Sn) ) 603/577 Hz), 25.5 (C
2
3
,
3
13
119
SSn: C, 39.36; H, 6.60; S, 7.50; Sn, 27.79. Found: C, 39.10; H, 6.54;
S, 7.17; Sn, 27.25.
119
1
126.6 (Ph). Sn{ H} NMR (149.21 MHz, CDCl
3
): δ -231.7. IR
(Nujol, cm-1): 1280, 1135, 1050 (ν(SO
)), 1520 (ν(CO)). Mass
2
n-Pr Sn(bzac)OS(O)
2
Me (7). The reaction of methoxydi-n-propyltin
3
+
+
methanesulfonate (1) (0.64 g, 1.94 mmol) and benzoylacetone (0.31 g,
spectrum (EI, 70 eV): m/z 495 [M - i-Bu] , 343 [Sn(bzbz)] , 215
+
1
5
7
8
.94 mmol) was carried out in a manner similar to that described for
[SnOSO
2
Me] . Anal. Calcd for C24
H
32
5
O SSn: C, 52.28; H, 5.85; S,
. Compound 7 was isolated as a pale yellow solid. Yield: 0.69 g,
5.81; Sn, 21.53. Found: C, 51.92; H, 5.80; S, 5.62; Sn, 20.88.
Preparation of (µ-Hydroxo)diorganotin Methanesulfonates (12-
14). In a typical procedure, methoxydi-n-propyltin, methoxydi-n-
butyltin, or methoxydiisobutyltin methanesulfonate (1, 2, or 3) (1.32,
1.43, or 1.43 g; 4.00 mmol) was dissolved in ∼50 mL of moist methanol
(95:5 methanol/water) and the clear solution was stirred under
atmospheric conditions for 24 h. Thereafter, solvent was stripped off
under vacuo. To the resulting viscous mass was added a mixture of
n-hexane and solvent ether (4:1) with constant stirring. A white solid
was obtained in each case, which was filtered off, washed with solvent
ether, and dried under vacuo. Recrystallization of the product from a
1
7.5%. H NMR (300 MHz, CDCl
3
): δ 2.88 (s, 3H, SCH
3
), 1.82 (m,
H, SnCH
CO), 7.43-7.93 (m, 5H, Ph). C{ H} NMR (100.61 MHz,
2 2 3
CH ), 1.04 (t, 6H, CH ), 6.18 (s, 1H, CH), 2.21 (s, 3H,
1
3
1
CH
CDCl
3
1
13
119/117
3
): δ 38.6 (SCH
3
), 28.6 (C
, J( C- Sn) 36 Hz), 16.8 (C
85.0, 194.7 (CO), 97.3 (CH), 27.4 (dik CH
1
, J( C-
Sn) ) 621/595 Hz),
13 119
2
13
119
3
1
1
1
7.2 (C
2
3
, J( C- Sn) ) 96 Hz),
), 135.4, 132.0, 127.7,
26.9 (Ph). Sn{ H} NMR (149.21 MHz, CDCl ): δ -239.9. IR
3
1
19
1
3
(
Nujol, cm-1): 1250, 1130, 1050 (ν(SO
3
)), 1520 (ν(CO)). Mass
+
+
spectrum (EI, 70 eV): m/z 419 [M - Pr] , 367 [M - OSO
2
Me] , 301
+
+
[
Pr
C, 44.27; H, 5.68; S, 6.95; Sn, 25.74. Found: C, 44.11; H, 5.57; S,
.82; Sn, 25.54.
n-Bu Sn(bzac)OS(O)
2 2 26 5
SnOS(O) Me] , 281 [Sn(bzac)] . Anal. Calcd for C17H O SSn:
CH
methanesulfonate (12, 13, or 14).
n-Pr Sn(OH)OS(O) Me (12). The compound was obtained as a
white solid. Yield: 0.81 g, 64.2%. H NMR (300 MHz, CDCl
2.85 (s, 3H, SCH ), 1.81 (m, 8H, SnCH CH ), 1.10 (t, 6H, CH ), 4.85
(br, 1H, OH). C{ H} NMR (100.61 MHz, CDCl ): δ 39.5 (SCH ),
32.5, 31.7, 30.3, 29.7, 29.4, 27.5, 18.6, 18.3 (SnCH
2 2
Cl /n-hexane mixture afforded the corresponding hydroxodialkyltin
6
2
2
Me (8). This compound was isolated as a pale
2
2
1
yellow solid from the reaction of 2 (0.70 g, 1.94 mmol) and
benzoylacetone (0.31 g, 1.94 mmol) by following a procedure similar
to that described for 5. Yield: 0.72 g, 75.5%. H NMR (300 MHz,
3
): δ
3
2
2
3
1
13
1
3
3
1
19
CDCl
3
): δ 2.90 (s, 3H, SCH
H, CH ), 0.90 (t, 6H, CH ), 6.20 (s, 1H, CH), 2.25 (s, 3H, CH
.40-7.96 (m, 5H, Ph). C{ H} NMR (100.61 MHz, CDCl
13
3
), 1.76 (m, 8H, SnCH
2
CH
2
), 1.40 (m,
CO),
): δ 39.7
2 2 3
CH CH ). Sn-
1
4
7
2
3
3
{ H} NMR (149.21 MHz, CDCl
3
): δ -188.2, -182.9, -176.4, -175.6,
1
3
1
-1
3
-169.9, -163.1. IR (Nujol, cm ): 1280, 1250, 1200, 1140, 1065,
1
13
119/117
2
(SCH
3
), 26.9 (C
1
, J( C-
Sn) ) 615/589 Hz), 28.4 (C
2
, J( C-
1040 (ν(SO
+ +
2 2 2 2
[PrSn(OSO Me) ] , 311 [HSn(OSO Me) ] , 301 [M - OH] , 215
3
)), 3350 (ν(OH)). Mass spectrum (EI, 70 eV): m/z 353
1
19
3
13
119
+
Sn) ) 34 Hz), 26.3 (C
3
, J( C- Sn) ) 99 Hz), 13.5 (C ), 186.1,
4