Kinetic and thermodynamic studies of carbon monoxide insertion
in alkylosmium(II) complexes and comparison
with iron(II) and
ruthenium(II) isoelectronic
complexes
Abstract
The equilibrium constants of the reaction of
cis,trans-[Os(CO)
2
(PMe
3
)
2
(Me)I] 1c with carbon monoxide to give
cis,trans-[Os(CO)
2
(PMe
3
)
2
(COMe)I] 2c have been measured and compared with the
values obtained for the isoelectronic complexes of iron and ruthenium.
The kinetics of the above reaction as well as of the analogous insertion
reaction with C
6
H
11
NC, which affords
trans-[Os(CO)(PMe
3
)
2
(C
6
H
11
NC)(COMe)I] 3, has been investigated. The results are
interpretable by the methyl migration mechanism. The crystal structure
of the new complex 3 has been determined. Furthermore, the
isomer
trans,trans-[Os(CO)
2
(PMe
3
)
2
(Me)I] 1t has been synthesized by the photochemical
isomerization of 1c in the solid state. The spectroscopic
properties of the cis,trans (c) and
trans,trans (t) isomers for the triad Fe, Ru
and Os are compared.
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