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Synlett 2004(2): 0371-0373  
DOI: 10.1055/s-2004-815402
LETTER
© Georg Thieme Verlag Stuttgart · New York

Simple Synthesis of Tetrabutylammonium and Potassium Salts of Difluorotriorganostannate and Silicate Anions

Robert Bujok, Mieczysław Mąkosza*
Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw 42, POB 58, Poland
Fax: +48(22)6326681; e-Mail: icho-s@icho.edu.pl;
Further Information

Publication History

Received 7 November 2003
Publication Date:
12 January 2004 (online)

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Abstract

The title salts are readily prepared via stirring of trior­ganotin halides or triorganosilyl fluorides with tetrabutylammonium hydrogen sulfate and potassium, fluoride or sole potassium fluoride.

Key words

tin compounds - silicon compounds - germanium compounds - hypervalent anions

9

Mkosza, M., Bujok, R., manuscript in preparation.

10

Synthesis of Tetrabutylammonium Salts
KF (10-20 equiv, see Table [1] ), R3MX (3.0 mmol), tetrabutylammonium hydrogensulphate (3.0 mmol) and solvent (7.5 mL) were placed in flask and heated with stirring at 60 ºC for 24 h. The solid was filtered off and washed with the solvent used in the reaction (4 × 5 mL). The combined filtrates were evaporated and the residue was recrystallized from MeCN-Et2O, compounds 1 and 2 were isolated as oils and not purified.
Synthesis of Potassium Salts KF (10-20 eq; see Table [2] ), R3MX (1.0 mmol) and DMF (2.5 mL) were placed in flask and heated with stirring at 60 ºC for 24 h. The solid was filtered off and washed with DMF (4 × 3 mL). The combined filtrates were evaporated and the residue was recrystallized from DMF-Et2O.
1: Oil. 1H NMR (DMSO-d 6 ): δ = 0.01 (9 H), [Sn satellites:
J (119Sn-1H) = 74.8 Hz, J (117Sn-1H) = 71.5 Hz], 0.94 (t, J = 7.2 Hz, 12 H), 1.21-1.40 (m, 8 H), 1.49-1.62 (m, 8 H), 3.12-3.20 (m, 8 H). 19F NMR (CDCl3): δ = -126.7. 119Sn NMR (CDCl3): δ = -53.7. MS [LSIMS(-) NBA]: m/z calcd for Me3 120SnF2 -: 203; found: 203.
2: Oil. 1H NMR (DMSO-d 6 ): δ = 0.68 (m, 6 H), 0.84 (t, J = 7.2 Hz, 9 H), 0.94 (t, J = 7.2 Hz, 12 H), 1.15-1.40 (m, 14 H), 1.42-1.69 (m, 14 H.), 3.14-3.23 (m, 8 H). 19F NMR (CDCl3): δ = -146.3. 119Sn NMR (CD3CN): δ = -107.9. MS [LSIMS (-) NBA]: m/z calcd for Bu3 120SnF2 -: 329; found: 329.
3: mp 189-190.5 ºC (lit.1 189-189.5 ºC). 19F NMR (CDCl3): δ = -162.93 (s), [Sn satellites: J (119Sn-19F) = 1985 Hz, J [117Sn-19F] = 1896 Hz]. Anal. Calcd for C34H51N1F2Sn: C, 64.77; H, 8.15; N, 2.22. Found: C, 64.79; H, 8.22; N, 2.04.
4: mp 148-150 ºC (lit.2 150-151 ºC). 19F NMR (CDCl3): δ = -96.1, [Si satellites: J [29Si-19F] = 250 Hz]. Anal. Calcd for C34H51N1F2Si: C, 75.64; H, 9.52; N, 2.59. Found: C, 75.50; H, 9.52; N, 2.47.
5: mp 162-164 ºC. 1H NMR (CDCl3): δ = 0.89 (t, J = 6.9 Hz, 12 H); 1.20 (br s, 16 H); 2.74 (br s, 8 H), 7.27 (br s, 5 H, Ph). 19F NMR (376 MHz, CDCl3): δ = -118.9 (br s). MS [ESI
(-), MeCN]: m/z calcd for Ph3GeF2 -: 341; found: 341.2. Anal. Calcd for C34H51N1F2Ge: C, 69.88; H, 8.80; N, 2.40. Found: C, 69.62; H, 8.80; N, 2.28.
6: mp 136-137 ºC. 1H NMR (CDCl3): 0.85 (t, J = 6.8 Hz, 12 H), 0.98-1.12 (m, 16 H), 2.26 (s. 9 H), 2.40-2.48 (m, 8 H), 7.05 (6 H), 7.93 [Sn satellites: J (119Sn-1H) = 70 Hz, J (117Sn-1H) = 55 Hz; 6 H). 19F NMR (CDCl3): δ = -161.2 [Sn satellites: J (119Sn-19F) = 1942 Hz, J [117Sn-19F] = 1857 Hz). 119Sn NMR (CDCl3): δ = -333.4 [t, J (119Sn-19F) = 1938 Hz). MS [LSIMS (-) NBA]: m/z calcd for (4-MePh)3 120SnF2 -: 431; found: 431.5.
7: mp 136-138 ºC. 1H NMR (DMSO-d 6 ): δ = 0.92 (t, J = 7.2 Hz, 12 H), 1.26-1.36 (m, 8 H), 1.44-1.58 (m, 8 H), 2.21 (s, 9 H), 3.08-3.12 (m, 8 H), 6.91, 7.74 (AA′XX′, 12 H). 19F NMR (DMSO-d 6 ): δ = -97.7 [Si satellites: J [29Si-19F] = 254 Hz, MS [ESI(-) MeCN]: m/z calcd for (4-MePh)3SiF2 -: 339; found: 339. Anal. calcd for C37H57N1F2Si: C, 76.36; H, 9.87; N, 2.41. Found C, 76.13; H, 10.13; N, 2.34.
8: mp 138-140 ºC. 1H NMR (DMSO-d 6 ): δ = 0.93 (t, J = 7.4 Hz), 1.25-1.34 (m, 8 H), 1.50-1.59 (m, 8 H), 3.12-3.154 (m, 8 H), 7.18, 7.96 (AA′XX′, 12 H). 19F NMR (DMSO-d 6 ): δ = -97.6 [Si satellites: J (29Si-19F) = 255 Hz]. MS [ESI (-) MeCN]: m/z calcd for (4-35ClPh)3SiF2 -: 399; found: 399.
9: mp > 250 ºC. 1H NMR (400 MHz, DMSO-d 6 ): δ = 7.25 (br s, 9 H), 7.94 [Sn satellites: J (117,119Sn-1H) = 64 Hz, 6 H). 19F NMR (376 MHz, DMSO-d 6 ): δ = -164.3 [Sn satellites: J (Sn-F) = 2021 Hz]. 119Sn NMR (DMSO-d 6 .): δ = -350.0 [t, J [119Sn-19F] = 1938 Hz). MS [LSIMS (-) NBA]: m/z calcd for Ph3 120SnF2 -: 389; found: 389. Anal. Calcd for C18H15F2KSn: C, 50.62; H, 3.54 Found C, 50.25; H, 3.83.
10: mp 225 ºC (decomp.). 1H NMR (400 MHz, DMSO-d 6 ): δ = 7.10-7.13 (m, 5 H), 7.31-7.36 (m, 3 H), 7.41-7.44 (m, 4 H), 7.85-7.88 (m, 3 H). 19F NMR (376 MHz, DMSO-d 6 ):
δ = -98.2. Anal. Calcd for C18H15F2KSi: C, 64.25; H, 4.49. Found C, 64.51; H, 4.71.
11: mp > 250 ºC. 1H NMR (400 MHz, DMSO-d 6 ): δ = 2.26 (s, 9 H), 7.08 (br s, 6 H), 7.80 (br s, 6 H). 19F NMR (376 MHz, DMSO-d 6 ): δ = -162.9 [Sn satellites: J (117,119Sn- 19F) = 2020 Hz, 117Sn NMR (DMSO-d 6 ): δ = -346.8 [t, J (117Sn-19F) = 1929 Hz]. MS [ESI (-) MeCN]: Calcd for
(4-MePh)3 120SnF2 -: 431; found 431.3. Anal. calcd for C21H21F2KSn: C, 53.67; H, 4.51. Found C, 52.97; H, 4.53.
12: mp > 250 ºC. 1H NMR (400 MHz, DMSO-d 6 ): δ = 7.32 (br s, 6 H), 7.97 [Sn satellites: J (117,119Sn-1H) = 53 Hz, 6 H). 19F NMR (37 MHz, DMSO-d 6 ): δ = -164.3 [Si satellites: J (119Sn-19F) = 2089 Hz, J (117Sn-19F) = 1997 Hz]. 117Sn NMR (DMSO-d 6 .): δ = -353.5 [t, J (117Sn-19F) = 1997 Hz]. MS [ESI (-) MeCN]: m/z calcd for (4-35ClPh)3 120SnF2 -: 491.0; found: 491.0. Anal. Calcd for C18H12Cl3F2KSn: C, 40.76; H, 2.28. Found C, 41.40; H, 2.74
13: mp 164 ºC (decomp.). 1H NMR (400 MHz, DMSO-d 6 ): δ = 7.16-7.21 (m, 3 H), 7.48-7.54 (m, 6 H), 7.84-7.90 (m, 3 H). 19F NMR (376 MHz, DMSO-d 6 ): -97.6 [Si satellites: J [29Si-19F] = 256 Hz]. Anal. Calcd for C18H12Cl3F2KSi: C, 49.15; H, 2.75. Found C, 49.08; H, 3.04.