Abstract LiAlH
4
and AlCl
3
reacted in a ratio 1:3 to obtain Cl
2
AlH, which is stabilised by the addition of two equivalents of N-methylpiperidine (nmp) to form dichloroalane (
1
) as bis adduct of nmp. Compound
1
was allowed to react with 2,6-
t
Bu-4-MeC
6
H
2
OH and HO
c
Hex in a 1:1 ratio to get compounds
2
and
3
, respectively. Cl
2
Al(2,6-
t
Bu-4-MeC
6
H
2
O)(nmp) (
2
) is a monomer in which the central aluminium atom is tetracoordinate. Contrary to the parent compound
1
, compound
2
is stabilised by only one nmp molecule. The larger bulk of the alkoxide in
2
prevents the second nmp molecule to reach the aluminium atom. Compound
3
crystallises as unique anionic tri-nuclear aluminium entity [Al
3
Cl
6
(O
R
)
4
]
–
[nmp
2
H]
+
with a protonated nmp as countercation. The lesser bulk of the cyclohexanolate leads to a higher oligomerisation of
R
OAlCl
2
(
R
= cyclohexyl). When a relatively bulkier alcohol, 1-methylcyclohexanol, was allowed to react with mixtures of LiAlH
4
and AlCl
3
prepared in 1:1 and 1:3 ratios in solution, compounds
4
and
5
, respectively, were obtained. Both compounds ((HClAlO
R
)
2
(
4
) and (Cl
2
AlO
R
)
2
(
5
),
R
=
c
HexMe-1)) are dimers with oxygen as bridging atom in the Al
2
O
2
rings. All compounds
2
,
3
,
4
, and
5
were structurally characterised by X-ray diffraction on single crystals.