C. Santamaria et al., Reactions of the titanaallene intermediate [Cp*Ti-2=C=CH2] with isonitriles: An approach to the chemistry of radialene type molecules, ORGANOMETAL, 20(7), 2001, pp. 1354-1359
The titanaallene intermediate [Cp*Ti-2=C=CH2] (2), obtained via methane eli
mination from Cp*Ti-2(CH=CH2)Me (1), reacts with an excess of cyclohexyliso
nitrile (CyNC), to give the five-membered metallacycle Cp*2TiC(=NCy)C(=NCy)
C(=CH2)C=NCy (4), which exhibits a radialene substructure. This reaction oc
curs by a [2+1] addition followed by subsequent insertion of two molecules
of isonitrile. A [2+1] addition product is isolated from the reaction of 1
with 2,6-dimethylphenylisonitrile (ArNC) in 1:2 ratio in the form of the az
abutatriene complex (Cp*Ti-2(CNAr)(eta (2)-H2CC=C=NAr) (5). The X-ray struc
ture analysis of 5 reveals a pentacoordinated geometry consisting of a eta
(2)-C,C-azabutatriene moiety stabilized by a further ArNC ligand. Whereas 5
is stable in the solid state (dec 102-105 degreesC), in solution (20 degre
esC) one molecule of isonitrile is released. Subsequent intramolecular C-H
bond activation and C-C bond formation afford product 7. The latter can be
directly isolated from reaction of 2 with 1 equiv of ArNC. The treatment of
the titanaallene species 2 with 3 equiv of ArNC leads, through the inserti
on of two isonitrile molecules into the Ti-CH2 bond in complex 5, to the fi
ve-membered ring complex 8, Cp*2TiC(=NAr)C(=NAr)CH2C=C=NAr. The molecular s
tructure of 8; shows a planar titanacyclopentane. Density functional theory
calculations confirm the terminal C,C-coordination mode as found in 5 as t
he preferred arrangement against the C,N- or internal C,C-coordination mode
s.