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Title: An Unusual Hydride-Bridged Aluminum Complex with a Square-Planar Tetraaluminum Core Stabilized by 2,5-Bis((Dimethylamino)methyl)pyrrole Ligands
Authors: Chang, Jr-Chiuan;Hung, Chen-Hsiung;Huang, Jui-Hsien
Contributors: 化學系
Date: 2001-10
Issue Date: 2012-12-10T01:39:24Z
Publisher: American Chemical Society
Abstract: The novel hydride-bridged tetranuclear aluminum
complex {AlH2[C4H2N(CH2NMe2)2-2,5]AlH3}2 (2)
and the related deuterium complex {AlD2[C4H2N(CH2-
NMe2)2-2,5]AlD3}2 (2-D) have been synthesized by reaction
of AlCl2[C4H2N(CH2NMe2)2-2,5] (1) with 2 equiv of
LiAlH4 or LiAlD4. The crystal structure of complex 2-D
reveals an unusual structure in which the aluminum
atoms are in a square-planar arrangement. Reaction of
2 with 2 equiv of H2O in diethyl ether affords the
aluminum dihydride complex [C4H2N(CH2NMe2)2-2,5]-
AlH2 (3).
Metal hydrides1 play an important role in catalytic
reactions due to their highly reactive metal-hydrogen
bonds. Among the metal hydrides, aluminum hydrides
are well-known and the topic has been reviewed.2
Hydride ions bound to aluminum atoms have been
observed in either terminal or bridging positions in
accord with varied auxiliary ligands in mononuclear,3
dinuclear,4 or trinuclear5 aluminum hydride complexes.
However, a hydride-bridged tetranuclear6 aluminum
complex has not been reported thus far. Currently, we
are interested in using the tridentate substituted pyrrole7
[C4H3N(CH2NMe2)2-2,5] as an auxiliary ligand in
early-transition-metal8 or group 13 metal complexes.9
We now report the synthesis and structural characterization
of a novel, hydride-bridged, tetranuclear aluminum
complex, which contains bis((dimethylamino)-methyl)pyrrole as a ligand. The reaction of compound
19 with 2 equiv of LiAlH4 in diethyl ether at 0 �C
generates compound 210 in 84% yield (eq 1).
Relation: Organometallics, 20(22): 4445-4447
Appears in Collections:[Department of Chemistry] Periodical Articles

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