Organoaluminum and -gallium Thiolates. 1. Synthetic and X-ray Structural Studies

Abstract

Organoaluminum and -gallium thiolates are prepared in high yield by the reaction of triorganoaluminum and -gallium derivatives with thiols. In this way, [Mes2Al(M-SBz)]2 (Mes = 2,4,6-Me3C6H2 8), and {Me2Ga[w-S(2,6-Me2CeH3)]}4 (9) were prepared and crystallographically characterized. The dimethyl-and dimesitylaluminum thiolates 1-3 were determined to be dimeric with four-membered (A1S)2 rings. The structure of 1 was determined in space group P2i/n (No.

Cyclopentadienylaluminum thiolates – synthesis and structure

“…Among these compounds aluminum alkoxides have been the most systematically and broadly examined (see for example [2]). Comparing to aluminum alkoxides the chemistry of thiolate derivatives is rather scant [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17]. The structures of organoaluminum thiolates are diversified and the factors controlling them are not still definitely examined.…”

Intramolekular schwefelstabilisierte Aluminium- und Galliumalkyle

“…The reaction of 5 and of 6 with BrMg(CH 2 ) 5 MgBr yields (CH 2 ) 5 Al(CH 2 ) 3 SEt (7) and (CH 2 ) 5 Ga(CH 2 ) 3 SEt (8), respectively. AlCl 3 and GaCl 3 react with two as well as three equivalents of ClMg(CH 2 ) 3 SEt forming ClAl[(CH 2 ) 3 SEt] 2 (9) and ClGa[(CH 2 ) 3 SEt] 2 (10) as well as Al[(CH 2 ) 3 SEt] 3 (11) and Ga[(CH 2 ) 3 SEt] 3 (12), respectively. The compounds were characterized by elemental analyses, mass spectroscopy, 1 H, 13 C, and 27 Al NMR investigations as well as 6 by single crystal X-ray structure analysis.…”

“…Der Chelatring weist eine Twist-Konformation um jene C±C-Bindung auf, die dem Galliumatom gegenu È berliegt. Der Ga±S-Abstand der koordinativen Bindung betra È gt 2,426 A Ê und ist damit trotz der Anwesenheit der elektronegativen Chlorsubstituenten am Gallium [9] etwas la È nger als die beschriebenen gemischt koordinativ-kovalenten Ga±S-Absta È nde in den oligomeren Organogalliumthiolaten [Ph 2 Ga(l-SEt)] 2 mit 2,379 A Ê [10], [R 2 Ga(l-S-c-C 5 H 9 )] 2 (R = Me, Ph) mit 2,388 A Ê [11], [Me 2 Ga(l-SC 6 H 3 -2,6-Me 2 )] 4 mit 2,397 A Ê [12] bzw. Iodogalliumthiolaten [I 2 Ga(l-SMe)] 2 mit 2,379 A Ê [13] und [I 2 Ga(l-S-i-Pr)] 2 mit 2,329 A Ê [14].…”

“…Die aufgrund des Chiralita Ètszentrums am Metallatom diastereotopen Methylenprotonen (CHH') 3 3 MgCl unter Bildung von Tris- [3-(ethylthio)propyl]aluminium (11) bzw. Tris- [3-(ethylthio)propyl]gallium (12). Die farblosen, mit zunehmender 3-(Ethylthio)propylsubstitution zunehmend viskoseren Flu È ssigkeiten ko È nnen nach Destillation unter vermindertem Druck etherfrei erhalten werden.…”

“…Analog zur Darstellung von 9 werden 7,04 g (40,0 mmol) Galliumtrichlorid in 100 ml Diethylether mit 74,1 ml einer 1,08 molaren Lo È sung von 3-(Ethylthio)propylmagnesiumchlorid (80,0 mmol) in Diethylether [6,7] Al[(CH 2 ) 3 SEt] 3 (11). Analog zur Darstellung von 9 werden 4,00 g (30,0 mmol) Aluminiumtrichlorid in 200 ml Diethylether mit 83,3 ml einer 1,08 molaren Lo È sung von 3-(Ethylthio)propylmagnesiumchlorid (90,0 mmol) in Diethylether [6,7] Ga[(CH 2 ) 3 SEt] 3 (12). Analog zur Darstellung von 9 werden 5,28 g (30,0 mmol) Galliumtrichlorid in 100 ml Diethylether mit 83,3 ml einer 1,08 molaren Lo È sung von 3-(Ethylthio)propylmagnesiumchlorid (90,0 mmol) in Diethylether [6,7] 3 J 7,6 Hz; 6 H, CH 2 Ga); 1,30 (t, 3 J 7,4 Hz; 9 H, CH 3 CH 2 S); 2,09 (m, 6 H, CH 2 CH 2 S); 2,48 (q, 3 J 7,4 Hz; 6 H, CH 3 CH 2 S); 2,65 ppm (t, 3 J 6,5 Hz; 6 H, CH 2 CH 2 S).…”