C2 Building blocks in the co-ordination sphere of electron-poor transition metals. Aspects of the chemistry of early-transition-metal carbenoide complexes
Abstract
Our understanding of the chemistry of the
transition-metal–carbon σ bond is improved by investigations
of the chemistry of alken-1-yl complexes of electron-poor transition
metals. There is no other system known in which we can easily switch
between the possible reaction pathways, depending on the nature of the
metal, the ligands L and the alken-1-yl group. Only reductive
elimination, α- and β-H elimination reactions give high
selectivity. α-Hydrogen elimination from
Cp*
2
Ti(CH![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
CH
2
)R
(Cp* = η-C
5
Me
5
) derivatives
leads to the versatile titana–allene intermediate
[Cp*
2
TiCCH
2
] 8. A wide range of
cycloaddition products of high thermal stability can be prepared using
8. In reactions of 8 with copper and gold complexes, heterodinuclear
µ-vinylidene compounds,
Cp*
2
Ti(µ-CCH
2
)(µ-
X)M′L, are formed. Additionally the first examples of
intermolecular carbene–carbene coupling reaction of a Fischer- and
a Schrock-carbene ligand are reported by using the strong nucleophilic
vinylidene fragment 8.
CH
2
)R
(Cp* = η-C
5
Me
5
) derivatives
leads to the versatile titana–allene intermediate
[Cp*
2
TiCCH
2
] 8. A wide range of
cycloaddition products of high thermal stability can be prepared using
8. In reactions of 8 with copper and gold complexes, heterodinuclear
µ-vinylidene compounds,
Cp*
2
Ti(µ-CCH
2
)(µ-
X)M′L, are formed. Additionally the first examples of
intermolecular carbene–carbene coupling reaction of a Fischer- and
a Schrock-carbene ligand are reported by using the strong nucleophilic
vinylidene fragment 8.
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