Synthesis of a Hexadentate Hexameric Aluminum Imide and Its Metathesis Reactions

The reaction of AlH 3 ·NMe 3 with one equivalent of 2‐cyanothiophene in toluene afforded [HAlNCH 2 (C 4 H 3 S)] 6 ( 2 ) in good yield. Treatment of 2 with SiMe 3 Br and SiMe 3 Cl in toluene under refluxing conditions resulted in the formation of compounds [BrAlNCH 2 (C 4 H 3 S)] 6 ( 3 ) and [ClAlNCH 2 (C 4 H 3 S)] 6 ( 4 ), respectively. In a similar way [PhC≡CAlNCH 2 (C 4 H 3 S)] 6 ( 5 ) was readily obtained from the reaction between 2 and PhC≡CH. When 2 was treated with PhSH the Al‐N cluster core dissociated and a four‐membered ring compound [(PhS) 2 AlNHCH 2 (C 4 H 3 S)] 2 ( 6 ) was formed. In contrast, a similar hexameric aluminum imide (HAlNCH 2 Ph) 6 ( 1 ) retains its Al‐N network when treated with PhSH to yield (PhSAlNCH 2 Ph) 6 ( 7 ). An exchange of ethyl groups and hydrides occurred when 2 was treated with excess of ZnEt 2 , forming [EtAlNCH 2 (C 4 H 3 S)] 6 8 . Compounds 2 − 4 and 6 − 8 were characterized by X‐ray single‐crystal analysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)