Following literature routes/^ a solution of [AICI3] (0.22 g, 1.60 mmol) in
diethyl ether (10 cm^) was added dropwise to a stirred slurry of [L1A1H4] (0.19 g, 5.0
mmol) in diethyl ether (15 cm^). 2 ,6-Me2C6H3SH (0.88 cm^, 6.65 mmol) was added
dropwise was added dropwise with stirring and immediate evolution o f hydrogen was observed. The resulting grey slurry was stirred at room temperature for 24 hours. After filtering through Celite the solvent was reduced under vacuum to approximately 5 cm^. Cooling to -20 °C afforded colourless crystals of 58 (1.09 g, 28% yield), mp 103-104 °C. Anal. Calc, for C2 8H3 7OS3AI: C, 65.59; H, 7.27. Found:
C, 63.51; H, 7.41. NMR 0/ppm (CDCI3): Ô 1.12 ( t , J = 11 Hz, 6H, 0 (CH2C //3)2), 1.35 (t, J = 11 Hz, 4.5H, 0 (CH2C //3)2), 2.25 (s, 18H, SC6H3(C7 7 3)2), 3.42 (q, 21 Hz, 4H, 0 (C//2CH3)2), 4.37 (q, J = 21 Hz, 2H, 0 (C i/2CH3)2), 6.77-6.95 (m, 9H, S C Æ (C H3)2). ^^C{'H} NMR (CDCI3): 6 13.4 (s, 0 (CH2CH3)2), 15.1 (s, 0 (CH2CH3)2), 23.6 (s, SC em C R^)!), 65.8 (s, 0 (CH2CH3)2), 6 8 . 8 (s, 0 (CH2CH3)2), 125.5 (s, m-SC6H3(CH3)2), 127.5 (s, # o - S C6H3(CH3)2), 132.4 (s, p-SC6H3(CH3)2), 142.0 (s, o-SC6H3(CH3)2). IR (KBr disc, cm '): 3057 m, 2977 m, 2922 w, 1460 s, 1436 m, 1371 m, 1323 w br, 1262 w, 1188 m, 1162 m, 1149 m, 1088 m, 1051 s, 1009 s, 989 m, 878 s, 831 w, 760 vs, 718 s, 588 m, 528 s, 496 s, 480 s, 413 m.
3.4.11 Preparation of [Li(OEt2)3] [Al(SC6H3Me2-2,6)4] (59)
Following literature routes,''^ a solution of [AICI3] (0.22 g, 1.60 mmol) in
diethyl ether (10 cm^) was added dropwise to a stirred slurry of [L1A1H4] (0.19 g, 5.0
mmol) in diethyl ether (15 cm^). 2,6-Mc2C6H3SH (0.88 cm^, 6.65 mmol) was added
dropwise with stirring and immediate evolution of hydrogen was observed. The resulting grey slurry was stirred at room temperature for 24 hours. After filtering through Celite the solvent was reduced under vacuum to approximately 5 cm^. Cooling to -20 °C afforded colourless crystals of 59 (0.24 g, 25% yield), decomposed without melting below 230 °C. Anal. Calc, for C4 4H6 6 0 3S4LiAl: C, 65.63; H, 8.26.
Found: C, 63.71; H, 7.51. 'H NMR 0/ppm (CDCI3): ô 2.00 (t, J = 14 Hz, 0 (CH2C //3)2), 2.27 (s, 24H, SC6H3(C7^ )2), 3.53 ( q , J = 2 l Hz, 0 (C7^C H3)2), 6 .8 6-
(s, SC6H3( Œ 3)2), 66.0 (s, 0(Œ2CH3)2), 125.0 (s, w-SC6H3(CH3)2), 127.1 (s, ipso-
SC6H3(CH3)2), 134.8 (s, p-SC6H3(CH3)2), 142.3 (s, o-SC6H3(CH3)2). IR (KBr dise, cm"'): 1583 w, 1303 w, 1257 w, 1161 wm 1092 m, 1051 s, 1022 m, 912 m, 838 w, 798 m, 771 s, 759 m, 587 m, 521 m, 492 m, 468 m, 436 m, 408 m.
3.4.12 Preparation of [Al(SC6H3Me2-2,6)3(HSC6H3Me2-2,6)] (60)
2,6-Mc2C6H3SH (0.3 cm^, 2.26 mmol) was added dropwise to a solution of [AlH3(NMe2Et)] (0.3 cm^, 2.26 mmol) in diethyl ether (15 cm^) with stirring at room
temperature. Evolution of hydrogen was observed and a white precipitate formed. The solvent was removed under vacuum yielding a white powder (0.39 g, 97% yield). Recrystalisation from a minimum of CH2CI2 yielded colourless crystals of 60
suitable for X-ray crystallography. Anal. Calc, for C3 6H4 8NS4AI: C, 67.13; H, 7.30;
N, 1.78. Found: C, 64.20; H, 6.72; N, 1.35. 'H NMR 5/ppm (CD2CI2): 5 1.10 (t, J = 1 1 Hz, NCH2C //3), 1.17 (t, J = 11 Hz, NCH2C //3), 2.14 (s, SC6H3(C//3)2), 2.29 (s, SC6H3(C773)2), 2.34 (s, SC6H3(C7/3)2), 2.36 (s, SC6H3(C7/3)2), 2.38 (s, SC6H3(C773)2), 2.45 (s, (0 7 /3)2), 2.73 (s, N(C7/3)2), 2.77 (q, J = 19 Hz, NC7/2CH3), 3.31 (q, J = \9 Hz, N C //2CH3), 6.86-7.01 (m, 9H, SC6/ /3(CH3)2). '^C('H} NMR (CDCI3): 5 6.0 (s, NCH2CH3), 9.9 (s, NCH2CH3), 23.8 (s, SC6H3(CH3)2), 24.1 (s, SC6H3(CH3)2), 42.7 (s, NCH2CH3), 43.2 (s, NCH2CH3), 51.8 (s, N(CH3)2), 125.2 (s, m-SC6H3(CH3)2), 126.0 (s, m-SC6H3(CH3)2), 127.3 (s, zp5u-SC6H3(CH3)2), 127.9 (s, ipso- SC6H3(CH3)2), 133.1 (s, ;2-SC6H3(CH3)2), 136.2 (s, ;?-SC6H3(CH3)2), 142.8 (s, o- SC6H3(CH3)2). IR (nujol, cm"'): 3143 m, 1581 m, 1375 s, 1161 m, 1115 m, 1082 w, 1062 s, 1021 m, 988 s, 914 s, 812 m, 764 vs, 720 s, 586 s, 544 s, 469 s, 458 m, 442 w. 3.5 References
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