Synthesis of a Hexadentate Hexameric Aluminum Imide and Its Metathesis Reactions

Abstract

The reaction of AlH3·NMe3 with one equivalent of 2‐cyanothiophene in toluene afforded [HAlNCH2(C4H3S)]6 (2) in good yield. Treatment of 2 with SiMe3Br and SiMe3Cl in toluene under refluxing conditions resulted in the formation of compounds [BrAlNCH2(C4H3S)]6 (3) and [ClAlNCH2(C4H3S)]6 (4), respectively. In a similar way [PhC≡CAlNCH2(C4H3S)]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)2AlNHCH2(C4H3S)]2 (6) was formed. In contrast, a similar hexameric aluminum imide (HAlNCH2Ph)6 (1) retains its Al‐N network when treated with PhSH to yield (PhSAlNCH2Ph)6 (7). An exchange of ethyl groups and hydrides occurred when 2 was treated with excess of ZnEt2, forming [EtAlNCH2(C4H3S)]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)

Methyl Substitution of Aluminum−Hydride Bonds in a Carbaalane and an Aluminum Imide

“…CHN analyses were performed at the Analytical Laboratory of the Institute of Inorganic Chemistry at Göttingen, Germany. 6 ] (6): AlMe 3 (2.7 mL of a 2.0  solution in heptane, 5.40 mmol, 9.0 equiv.) was added dropwise to a solution of 3 (0.50 g, 0.60 mmol, 1.0 equiv.)…”

“…Filtering off these crystals and storing the solution at 4°C afforded additional crystals of the same shape. The Xray single crystal structure analysis showed these to be the expected compound [(AlMe) 6 6 ] (7), where the hydrides have been substituted by ethyl groups; no coordination of diethylzinc to the thiophenyl groups was found. The substitution of the hydridic hydrogens of hexameric aluminum imides, prepared from aluminum hydrides and primary amines, was first reported in the 1970s.…”

“…The aluminumϪhydride bonds in the hydroalumination products can be converted into other functionalities. Recently, we have used various reagents to substitute the hydrides in the carbaalane [(Al-H) 6 (AlNMe 3 ) 2 (CCH 2 R) 6 ] (R ϭ Ph 1, CH 2 SiMe 3 2) and in the aluminum imide [(AlH) 6 (NCH 2 C 4 H 3 S) 6 ] (3) to yield halogen and alkynyl derivatives.…”

“…The methylated compounds [(AlMe) 6 6 ] (6) were synthesized in good yields from the corresponding hydride derivatives by treatment with AlMe 3 in toluene. The X-ray single crystal structures…”

Synthesis and electrochemical behavior of the ferrocenyl units assembled on imidoalane and carbaalane clusters

“…Solvents were purified according to conventional procedures and were freshly distilled prior to use. Compounds 4 [14,15], 5 [16,17], 8 [13,18], ferrocenylnitrile [19], ferrocenylacetylene [20,21] and AIH 3 ' NMe3 [22] were prepared as described in the literature. IR spectra were recorded on a Bio-Rad Digilab FTS7 spectrometer.…”