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Synthesis of Aluminum Hydrazides by Hydroalumination of 2,3‐Diazabutadienes—Formation of an Al 4 (N 2 ) 3 Cage Compound and an Al 3 (N 2 ) 3 Macrocyclic Ligand
Author(s) -
Uhl Werner,
Molter Jens,
Neumüller Bernhard
Publication year - 2001
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20010401)7:7<1510::aid-chem1510>3.0.co;2-p
Subject(s) - chemistry , sublimation (psychology) , crystallography , octahedron , amide , lone pair , ligand (biochemistry) , adduct , metal , aluminium , molecule , medicinal chemistry , stereochemistry , crystal structure , organic chemistry , psychology , biochemistry , receptor , psychotherapist
Treatment of 1,1,4,4‐tetramethyl‐2,3‐diazabutadiene with the alane adduct [AlH 3 (NMe 2 Et)] yielded the hydrazine derivative (AlH 2 ) 2 (AlH) 2 (N 2 i Pr 2 ) 3 ( 1 ) by the hydroalumination of both C−N double bonds. Compound 1 has a complicated cage structure formed by three hydrazido groups and four aluminium atoms. As a particularly interesting structural motif it contains a N−N group side‐on‐coordinated to one aluminium atom through its lone pairs of electrons. Sublimation of 1 gave a heterocubane‐type compound (HAlN i Pr) 4 ( 2 ) by the complete cleavage of all N−N bonds, one face of which is bridged by weakly coordinated diisopropyldiazene with a N−N double bond. Repeated sublimation gave the pure, unsupported heterocubane molecule 3 . Heating of the rough product of the reaction of alane and diazabutadiene to 90 °C in a closed vessel yielded another product Al(AlH 2 ) 3 (N 2 i Pr 2 ) 3 ( 4 ), which contains a cyclic chelating ligand formed by three hydrazido groups and three aluminium atoms. This heterocycle coordinates a fourth aluminum atom in the molecular center by close contacts to all six nitrogen atoms. A strongly flattened, distorted octahedral coordination sphere results for the inner metal atom.