Mono- and bi-nuclear titanium imido complexes supported by aryloxide ligands: fine control by ortho substituents
Abstract
Reaction of the titanium imido complexes
[Ti(NR)Cl
2
(py)
3
]
(R = Bu
t
,
C
6
H
3
Me
2
-2,6 or
C
6
H
3
Pr
i
2
-2,6;
py = pyridine) with 2 equivalents of lithium aryloxide
Li[OC
6
H
3
R′
2
-2,6]
(R′ = Me, Pr
i
or Bu
t
) afforded
the mononuclear four- or five-co-ordinate or binuclear four-co-ordinate
complexes
[{Ti(NR)(OC
6
H
3
R′
2
-2,6)
2
(py)
n
}
m
]
(m = 1, n = 1 or 2;
m = 2, n = 0) depending on
the identity of R and R′. The crystal structures of
[Ti
2
(µ-NBu
t
)
2
(OC
6
H
3
Me
2
-2,6)
4
] 1 and
[Ti(NC
6
H
3
Me
2
-2,6)(OC
6
H
3
Me
2
-2,6)
2
(py)
2
] have been
determined. Extended-Hückel molecular orbital calculations for
models of 1 showed that the deviation of the µ-imido
Bu
t
substituents from coplanarity with the
Ti
2
N
2
core in this and some related species can be
attributed to a second-order Jahn–Teller distortion.
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