SCHEDULED MAINTENANCE
Methyl–hydride metathesis between
[Zr(cp)2Me2] and
[HAl(µ3-NBut)]4: molecular
structures of
[Me1-xHxAl(µ
3-NBut)]4 (x = 0,
0.78 or 1) and [(cp)2ZrMe(µ-H)]2
(cp = η5-C5H5)
Abstract
The reaction of [Zr(cp)
2
Me
2
]
(cp = η
5
-C
5
H
5
) with
the cubane iminoalane,
[HAl(µ
3
-NBu
t
)]
4
, yielded
[(cp)
2
ZrMe(µ-H)]
2
and the alkyl-substituted
iminoalanes
[Al
4
MeH
3
(µ
3
-NBu
t
)
4
] 1 and
[Al
4
Me
2
H
2
(µ
3
-NBu
t
)
4
] 2. The dimer
[(cp)
2
ZrMe(µ-H)]
2
decomposes above
60 °C. The methyl–hydride exchange is first order with
respect to each reactant concentration, and
ΔH
‡
and
ΔS
‡
have been determined as
104(1) kJ mol
-1
and 18.8(4) J K
-1
mol
-1
, respectively. The molecular structures of
[(cp)
2
ZrMe(µ-H)]
2
,
[HAl(µ
3
-NBu
t
)]
4
,
[MeAl(µ
3
-NBu
t
)]
4
and a
cocrystallization disorder of compounds 1, 2 and
[HAl(µ
3
-NBu
t
)]
4
have been determined
by X-ray crystallography.
‡
and
ΔS
‡
have been determined as
104(1) kJ mol
-1
and 18.8(4) J K
-1
mol
-1
, respectively. The molecular structures of
[(cp)
2
ZrMe(µ-H)]
2
,
[HAl(µ
3
-NBu
t
)]
4
,
[MeAl(µ
3
-NBu
t
)]
4
and a
cocrystallization disorder of compounds 1, 2 and
[HAl(µ
3
-NBu
t
)]
4
have been determined
by X-ray crystallography.
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