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New Carbaalanes − (AlMe) 8 (CCH 2 Me) 5 (C≡C−Me) and the THF Adduct (AlMe) 8 (CCH 2 Me) 5 H·2THF
Author(s) -
Uhl Werner,
Breher Frank,
Mbonimana Alphonse,
Gauss Jürgen,
Haase Detlev,
Lützen Arne,
Saak Wolfgang
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200112)2001:12<3059::aid-ejic3059>3.0.co;2-z
Subject(s) - chemistry , adduct , medicinal chemistry , hydride , crystal structure , ether , hydrogen atom , crystallography , stereochemistry , ligand (biochemistry) , hydrogen , organic chemistry , group (periodic table) , biochemistry , receptor
The hydroalumination of Me 2 Al−C≡C−Me with a large excess of Me 2 AlH afforded the arachno ‐carbaalane (AlMe) 8 (CCH 2 Me) 5 H ( 4 ) by the release of AlMe 3 . 4 is almost insoluble in noncoordinating solvents and could not be purified by recrystallization. On an attempt to recrystallize 4 from a THF solution, the adduct (AlMe) 8 (CCH 2 Me) 5 H·2THF ( 5 ) was isolated as the first stable ether adduct of a carbaalane. Crystal structure determination revealed a cube of eight aluminium atoms, five faces of which are bridged by C−CH 2 Me groups. The sixth face is µ 2 ‐bridged by a hydrogen atom, and two opposite aluminium atoms of this face are coordinated by one THF ligand each. When the excess of dimethylaluminium hydride was reduced and the starting compounds were employed in a 1:2.1 molar ratio, an incomplete hydroalumination reaction led to the formation of the carbaalane (AlMe) 8 (CCH 2 Me) 5 (µ‐C≡C−Me) ( 6 ), in which the bridging hydrogen atom of 4 is replaced by an alkynido group. 27 Al NMR spectroscopic data of all the characterized carbaalanes are reported and supplemented by 27 Al NMR chemical shift calculations.