6158 Organometallics, Vol. 23, No. 26, 2004
Beckmann et al.
3); 4.0 mmol) in MeCN (20 mL) was added HO3SCF3 (600 mg,
4.0 mmol) via syringe. The mixture was stirred for 15 min to
give a clear solution. Solvent was removed in vacuo, and the
residue was recrystallized from hexane/CH2Cl2 (4 and 5) and
pentane/CH2Cl2 (6).
1H NMR (d3-MeCN): δ 7.8-7.0 (30H), 2.3 (4H). 13C NMR (d3-
MeCN): δ 140.9, 137.0, 136.0, 134.4, 133.4, 131.7, 131.0, 130.9,
129.2, 128.8, 128.5, 128.3, 128.1, 119.4 (CF3), 16.1 (1J(13C-119
-
Sn) ) 561 Hz, J(13C-119Sn) ) 32 Hz). 31P NMR (d3-MeCN):
δ 31.2 (2J(119Sn-O-31P) ) 91 Hz). 119Sn NMR (d3-MeCN): δ
-125.7 (2J(119Sn-O-31P) ) 90 Hz). Conductivity (c ) 3.33
mmol L-1 MeCN): 335 µS. Anal. Calcd for C39H34O5F3PSSn2
(940.20): C, 49.82; H, 3.64. Found: C, 49.89; H, 3.54. Mol wt
(c ) 10.0 mmol L-1 MeCN): 942.
2
4. Yield: 2.64 g, 91%. Mp: 152 °C dec. IR (KBr): ν 3587 s,
3065 m, 3052 m, 3017 w, 2994 w, 2959 w, 2904 w, 1641 br,
1578 m, 1483 m, 1431 s, 1334 w, 1292 s, 1218 s, 1175 s, 1072
m, 1026 s, 994 m, 911 w, 849 w, 803 w, 764 w, 727 s, 695 s,
660 m, 633 s, 586 w, 568 w, 513 w, 489 m, 467 m, 444 m cm-1
.
9. Yield: 1.35 g, 71%. Mp: 216-218 °C. IR (KBr): ν 3065
m, 3051 m, 2950 w, 2912 w, 2858 w, 1481 w, 1458 w, 1432 m,
1383 w, 1334 w, 1299 s, 1277 sh, 1229 s, 1188 m, 1164 w, 1130
s, 1068 m, 1045 m, 1025 s, 997 w, 892 w, 853 w, 730 s, 695 s,
628 m, 577 w, 547 s, 513 w, 449 m cm-1. 1H NMR (d3-MeCN):
δ 7.8-7.0 (30H), 0.8 (4H), 0.7 (2H). 13C NMR (d3-MeCN): δ
142.2, 137.0, 133.1, 131.9, 131.8, 130.9, 129.8, 129.5, 129.3,
119.5 (CF3), 26.9 (1J(13C-119Sn) ) 574 Hz, 3J(13C-119Sn) ) 42
Hz), 22.5 (2J(13C-119Sn) ) 38 Hz). 31P NMR (d3-MeCN): δ 30.6
(2J(119Sn-O-31P) ) 119 Hz). 119Sn NMR (d3-MeCN): δ -136.9
(2J(119Sn-O-31P) ) 120 Hz). Conductivity (c ) 3.33 mmol L-1
MeCN): 298 µS. Anal. Calcd for C40H36O5F3PSSn2 (954.23):
C, 50.35; H, 3.80. Found: C, 50.97; H, 3.86. Mol wt: not
measured due to poor solubility.
Synthesis of [Ph2(O2PPh2)Sn(CH2)nSn(O2PPh2)Ph2] (10-
12; n ) 1-3). [Ph2(OH)Sn(CH2)nSn(OH)Ph2] (1.19 mg for 10
(n ) 1), 1.21 g for 11 (n ) 2), 1.24 g for 12 (n ) 3); 2.00 mmol)
and HO2PPh2 (0.873 g, 4.00 mmol) in MeCN (20 mL) were
stirred at 80 °C for 18 h. The insoluble white precipitate was
isolated by filtration and dried under high vacuum.
10. Yield: 1.59 g, 80%. Mp: 257-259 °C. IR (KBr): ν 3046
m, 3012 w, 2990 w, 2898 w, 2850 w, 1480 w, 1432 m, 1330 w,
1303 w, 1259 w, 1178 sh, 1150 s, 1127 s, 1070 m, 1039 s, 1014
s, 995 m, 972 sh, 922 w, 846 w, 749 m, 727 s, 693 s, 664 m,
648 w, 610 w, 554 s, 544 s, 482 w, 451 m cm-1. Anal. Calcd for
C49H42O4P2Sn2 (994.29): C, 59.19; H, 4.26. Found: C, 59.21;
H, 4.33.
11. Yield: 1.69 g, 84%. Mp: 240-244 °C. IR (KBr): ν 3065
m, 3046 m, 3012 w, 2990 w, 2906 w, 1480 w, 1431 m, 1330 w,
1303 w, 1256 w, 1144 s, 1127 s, 1079 w, 1067 w, 1041 s, 1018
s, 998 m, 919 w, 751 w, 725 s, 693 s, 618 w, 551 s, 537 s, 451
m cm-1. Anal. Calcd for C50H44O4P2Sn2 (1008.32): C, 59.56;
H, 4.40. Found: C, 59.60; H, 4.37.
12. Yield: 1.74 g, 85%. Mp: 216-218 °C. IR (KBr): ν 3053
m, 3014 w, 2989 w, 2961 w, 2944 w, 2894 w, 2850 w, 1480 w,
1432 m, 1331 w, 1300 w, 1260 w, 1179 sh, 1146 s, 1128 s, 1068
m, 1043 s, 1021 s, 998 m, 929 w, 891 w, 848 w, 748 m, 728 s,
694 s, 672 m, 618 w, 551 s, 538 sh, 510 w, 451 m cm-1. Anal.
Calcd for C51H46O4P2Sn2 (1022.34): C, 59.92; H, 4.54. Found:
C, 59.95; H, 4.61.
Synthesis of [Ph2(OH)Sn(CH2)nSnPh2(O2PPh2)] (13-15;
n ) 1-3). [Ph2Sn(CH2)nSnPh2(OH)](O3SCF3) (594 mg for 13
(n ) 1), 608 mg for 14 (n ) 2), 622 mg for 15 (n ) 3); 1.00
mmol) and NaO2PPh2 (0.240 g, 1.00 mmol) were stirred in
MeCN (50 mL) at 80 °C for 18 h. An insoluble white precipitate
was isolated and washed with MeCN to remove any soluble
residue. The solid was dried under high vacuum.
13. Yield: 0.706 g, 89%. Mp: 192-196 °C. IR (KBr): ν 3436
vbr, 3052 m, 3016 w, 2988 w, 2964 w, 2923 w, 2853 w, 1629
br, 1581 w, 1544 w, 1511 w, 1479 w, 1429 w, 1305 w, 1261 w,
1215 w, 1132 s, 1071 w, 1038 s, 1016 m, 997 m, 967 w, 946 w,
909 w, 848 w, 806 w, 752 w, 727 s, 696 s, 660 w, 617 w, 551
m, 537 m, 480 w cm-1. Anal. Calcd for C37H33O3PSn2 (793.72):
C, 55.90; H, 4.10. Found: C, 55.98; H, 4.14. Mol wt: not
measured due to poor solubility.
14. Yield: 0.614 g, 76%. Mp: 188-191 °C. IR (KBr): ν 3432
vbr, 3062 w, 3047 w, 3014 w, 2989 w, 2929 w, 2901 w, 2854
w, 1479 w, 1428 m, 1377 w, 1331 w, 1304 w, 1257 w, 1157 s,
1129 s, 1073 w, 1045 s, 1022 m, 997 w, 923 w, 851 w, 828 w,
811 w, 753 m, 726 s, 694 s, 660 w, 618 w, 547 s, 499 w, 452 m
1H NMR (d3-MeCN): δ 7.3-7.0 (20H), 4.9 (1H), 2.1 (2H). 13C
NMR (d3-MeCN): δ 142.7 (1J(13C-119Sn) ) 740 Hz), 137.3,
131.4, 130.2, 121.9 (CF3), 23.0 (1J(13C-119Sn) ) 459 Hz). 119Sn
NMR (d3-MeCN): δ -116.0. Conductivity (c ) 3.33 mmol L-1
MeCN): 290 µS. Anal. Calcd for C26H23O4F3SSn2 (726.00): C,
43.02; H, 3.19. Found: C, 43.07; H, 3.15. Mol wt (c ) 13.0 mmol
L-1 MeCN): 705.
5. Yield: 2.52 g, 85%. Mp: 143 °C dec. IR (KBr): ν 3564 s,
3064 m, 3048 m, 3020 w, 2992 w, 2944 w, 2904 w, 1635 br,
1578 w, 1481 m, 1427 s, 1404 w, 1300 s, 1262 w, 1215 s, 1182
s, 1072 m, 1029 s, 997 m, 913 w, 886 m, 864 w, 773 sh, 735 s,
694 s, 660 w, 628 s, 574 w, 539 w, 513 w, 507 sh, 447 m, 421
1
m cm-1. H NMR (d3-MeCN): δ 7.6-7.0 (20H), 3.3 (1H), 2.1
(4H). 13C NMR (d3-MeCN): δ 142.9 (1J(13C-119Sn) ) 687 Hz),
137.1, 130.8, 129.7, 121.3 (CF3), 14.6 (1J(13C-119Sn) ) 599 Hz,
2
J(13C-119Sn) ) 30 Hz). 119Sn NMR (d3-MeCN): δ -139.7.
Conductivity (MeCN, c ) 3.33 mmol L-1): 369 µS. Anal. Calcd
for C27H25O4F3SSn2 (740.02): C, 43.82; H, 3.41. Found: C,
43.65; H, 3.34. Mol wt (c ) 13.0 mmol L-1 MeCN): 789.
6. Yield: 2.44 g, 81%. Mp: 149-152 °C dec. IR (KBr): ν
3567 s, 3065 m, 3052 m, 3017 w, 2994 w, 2959 w, 2904 w,
1641 br, 1578 m, 1483 m, 1431 s, 1334 w, 1292 s, 1218 s, 1175
s, 1072 m, 1026 s, 994 m, 911 w, 849 w, 803 w, 764 w, 727 s,
695 s, 660 m, 633 s, 586 w, 568 w, 513 w, 489 m, 467 m, 444
1
m cm-1. H NMR (d3-MeCN): δ 7.5-7.0 (20H), 3.9 (1H), 1.9
(4H), 0.8 (2H). 13C NMR (d3-MeCN): δ 142.5 (1J(13C-119Sn) )
676 Hz), 137.0, 130.7, 129.6, 121.3 (CF3), 23.2 (2J(13C-119Sn)
) 36 Hz), 21.9 (1J(13C-119Sn) ) 554 Hz, 3J(13C-119Sn) ) 14
Hz). 119Sn NMR (d3-MeCN): δ -102.7. Conductivity (c ) 3.33
mmol L-1 MeCN): 377 µS. Anal. Calcd for C28H27O4F3SSn2
(754.05): C, 44.60; H, 3.61. Found: C, 43.75; H, 3.66. Mol wt
(c ) 13.0 mmol L-1 MeCN): 774.
Synthesis of [Ph2Sn(CH2)nSnPh2(O2PPh2)](O3SCF3) (7-
9; n ) 1-3). To a suspension of [Ph2(OH)Sn(CH2)nSn(OH)-
Ph2] (1.19 g for 7 (n ) 1), 1.21 g for 8 (n ) 2), 1.24 g for 9 (n
) 3); 2.0 mmol) in MeCN (20 mL) was added HO3SCF3 (300
mg, 2.00 mmol) via syringe to give a clear solution after 5 min
of stirring at room temperature. Then, HO2PPh2 (0.436 g, 2.00
mmol) was added and the mixture stirred at 80 °C for 1 h.
The solvent was removed in vacuo. The residue was recrystal-
lized from hexane/CH2Cl2. The byproducts of 8 (323 mg, 0.32
mmol; 16%) and 9 (218 mg, 0.21 mmol; 11%) were filtered off
as insoluble solids after 2 days. The solvent was removed in
vacuo and the recrystallization repeated.
7. Yield: 1.04 g, 56%. Mp: 201-205 °C. IR (KBr): ν 3057
s, 1651 m, 1617 w, 1482 m, 1431 s, 1296 m, 1232 s, 1184 m,
1129 s, 1117 s, 1070 m, 1026 s, 1019 s, 995 m, 852 w, 751 sh,
730 s, 695 s, 659 w, 628 m, 605 w, 541 m, 502 w, 447 m, 401
1
w cm-1. H NMR (d3-MeCN): δ 7.8-7.0 (30H), 1.5 (2H). 13C
NMR (d3-MeCN): δ 140.9, 135.8, 133.6, 131.9, 131.9, 131.7,
131.0, 130.8, 129.5, 128.3, 128.1, 119.3 (CF3), 5.2 (1J(13C-119
Sn) ) 455 Hz). 31P NMR (d3-MeCN): δ 34.6 (2J(31P-O-117/119
-
-
Sn) ) 66 Hz). 119Sn NMR (d3-MeCN): δ -120.9 (2J(119Sn-O-
31P) ) 69 Hz). Conductivity (c ) 3.33 mmol L-1 MeCN): 344
µS. Anal. Calcd for C38H32O5F3PSSn2 (926.11): C, 49.28; H,
3.48. Found: C, 49.06; H, 3.68. Mol wt (c ) 10.0 mmol L-1
MeCN): 902.
8. Yield: 1.18 g, 63%. Mp: 169-171 °C dec. IR (KBr): ν
3066 s, 3051 sh, 1643 m, 1629 w, 1592 w, 1482 m, 1432 s,
1265 s, 1251 s, 1238 s, 1175 m, 1130 s, 1072 m, 1031 s, 993 m,
853 w, 753 sh, 729 s, 694 s, 636 m, 502 w, 447 m, 401 w cm-1
.