Aluminiumorganyle mit pentakoordiniertem Aluminium-Atom: Synthese und Molekülstrukturen von [AlX2{2,6-(NEt2CH2)2C6H3}] (X = Cl, Et, H)

✍ Scribed by Matthias Stender; Ulrike Segerer; Joachim Sieler; Evamarie Hey-Hawkins

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: German
• Weight: 124 KB
• Volume: 624
• Category: Article
• ISSN: 0372-7874
• DOI: 10.1002/(sici)1521-3749(199801)624:1<85::aid-zaac85>3.0.co;2-x

✦ Synopsis

Inhaltsu È bersicht. [Li{2,6-(NEt 2 CH 2 ) 2 C 6 H 3 }] 2 reagiert in guter Ausbeute mit AlCl 3 oder Et 2 AlCl zu [AlX 2 {2,6-(NEt 2 CH 2 ) 2 C 6 H 3 }] (X = Cl (1), Et (2)). 1 setzt sich mit NaH in Toluol zu [AlH 2 {2,6-(NEt 2 CH 2 ) 2 C 6 H 3 }] (3) um. Die Verbindungen 1±3 wurden spektroskopisch ( 1 H-, 13 C-, 27 Al-NMR, IR, MS) untersucht. Sie zeigen bei Raumtemperatur in Lo È sung dynamisches Verhalten ( 1 H-NMR), das sich fu È r 1 und 3 unterhalb von 278 K einfrieren la È ût. Demnach liegen bei tiefen Temperaturen monomere Moleku È le mit pentakoordinierten Al-Atomen vor, die ro È ntgenstrukturanalytisch auch fu È r 1 und 2 gezeigt werden konnten (1: monoklin, P2 1 /n, a = 9,7325(14), b = 13,552(5), c = 28,858(7) A Ê , b = 99,57(2)°, V = 3753(2) A Ê 3 , Z = 8, T = 223(2) K; 2: monoklin, C2/c, a = 15,0045(12), b = 9,2986(8), c = 14,9955(12) A Ê , b = 99,512(1)°, Z = 4, T = 223(2) K). Aluminium Organyls with Pentacoordinate Aluminium: Syntheses and Molecular Structures of [AlX 2 {2,6-(NEt 2 CH 2 ) 2 C 6 H 3 }] (X = Cl, Et, H) Abstract. The reaction of [Li{2,6-(NEt 2 CH 2 ) 2 C 6 H 3 }] 2 with AlCl 3 or Et 2 AlCl gives [AlX 2 {2,6-(NEt 2 CH 2 ) 2 C 6 H 3 }] [X = Cl (1), Et (2)] in good yield. 1 reacts with NaH in toluene to give [AlH 2 {2,6-(NEt 2 CH 2 ) 2 C 6 H 3 }] (3). 1±3 were characterised spectroscopically ( 1 H, 13 C, 27 Al n.m.r., i.r., mass spectroscopy). In solution at room temperature 1±3 exhibit dynamic behaviour. For 1 and 3 this can be frozen out below 278 K ( 1 H n.m.r.), indicating the presence of monomeric molecules with pentacoordinate Al at low temperature. Such species are also observed in the solid state as shown by an X-ray structure determination on 1 (monoclinic space group P2 1 /n, a = 9.7325(14), b = 13.552(5), c = 28.858(7) A Ê , b = 99.57(2)°, V = 3753(2) A Ê 3 , Z = 8, at 223(2) K) and 2 (monoclinic space group C2/c, a = 15.0045(12), b = 9.2986(8), c = 14.9955(12) A Ê , b =99.512(1)°, Z = 4, at 223(2) K).