Chemistry Reference
In-Depth Information
n
-heptane
! [MgfTi
2
OEt
8
Clg
-Cl
]
2
146
MgCl
2
C 2Ti
OEt
4
3
.
65
toluene
! [MfZr
2
OPr
i
8
Clg
-Cl
]
2
MCl
2
C 2Zr
OPr
i
4
3
.
66
where M D Be, Mg, Zn, Sn(
II
).
147
All the derivatives obtained in the above reactions are white crystalline solids,
dimeric in solution (benzene) except the beryllium derivative which also dimerizes
on ageing. The beryllium product was distilled at ¾190
Ž
C under 0.05 mm pressure
whereas under these conditions the magnesium derivative yielded a sublimate corre-
sponding in analysis to Mg
4
Zr
6
Cl
3
OPr
i
23
O
3
. All these products appear to be chloride
bridged, which is corroborated by the crystal structure of the Mg-Ti product.
146
Chloride alkoxides of Be, Mg, Zn and Sn(
II
) with Nb(
V
) have also been synthesized
by a similar series of reactions (Eqs 3.67 and 3.68):
148
benzene
!
68 hr
stir
MCl
2
C Nb
OPr
i
5
1
2
[fM
Nb
OPr
i
5
Cl
g
-Cl
]
2
3
.
67
MCl
2
C 2Nb
OPr
i
5
!
68 hr
stir
[MfNb
OPr
i
6
Clg
2
]
3
.
68
2.3
Synthesis of Higher Heterometallic Alkoxides and Allied Derivatives
Starting with bimetallic chloride (iodide) alkoxides synthesized by the general reaction
of Eq. (3.69):
MCl
x
C
y
KL ! MCl
x
y
L
y
C
y
KCl #
3
.
69
where
y
<
x
, a variety of heterotrimetallic and -tetrametallic alkoxides of Be,
7
lan-
thanons;
17
,
149
Zn and Cd;
150
,
151
Sn(
II
)and(
IV
);
152
,
153
Mn(
II
);
101
Fe(
II
);
109
Fe(
III
);
9
,
154
,
155
Co(
II
);
156
Ni(
II
);
157
Cu(
II
)
8
,
158
and Mg
159
can be synthesized as illustrated in a few
representative cases by Eqs (3.70) - (3.79):
-KCl
!fAl
OPr
i
4
gBefZr
2
OPr
i
9
g
fAl
OPr
i
4
gBeCl C KfZr
2
OPr
i
9
g
3
.
70
-KCl
!fZr
2
OPr
i
9
gMfAl
OPr
i
4
g
fZr
2
OPr
i
9
gMCl C KfAl
OPr
i
4
g
3
.
71
where M D Mn(
II
), Fe(
II
), Co(
II
), Ni(
II
).
-KCl
!fZr
2
OPr
i
9
gNifGa
OPr
i
4
g
fZr
2
OPr
i
9
gNiCl C KGa
OPr
i
4
3
.
72
-KCl
!fZr
2
OPr
i
9
gMfTa
OPr
i
6
g
fZr
2
OPr
i
9
gMCl C KTa
OPr
i
6
3
.
73
where M D Fe(
II
), Co(
II
).
-KCl
!fNb
OPr
i
6
gCofAl
OPr
i
4
g
fNb
OPr
i
6
gCoCl C KAl
OPr
i
4
3
.
74
