Variable-temperature 13C NMR does not show any
evidence for intramolecular ethylene rotation in
1-13C.
The rates of alkene dissociation for the propene (8)
and trans-2-butene (7) adducts of
Os2(CO)8 have been measured
in hydrocarbon solution and compared with the rates of alkene
dissociation from the corresponding
Os(CO)4(alkene)
adducts 6 and 9. The kinetic labilities of
propene and trans-2-butene are reversed in the
Os2(CO)8(alkene) and
Os(CO)4(alkene) systems; propene is replaced 2.5
times faster than trans-2-butene in the
Os2(CO)8(alkene) system,
while trans-2-butene is replaced 55.9 times faster than
propene in the Os(CO)4(alkene) system. We
have used
molecular mechanics to explore the reasons for this unusual reactivity
pattern and have found that these results may
be easily reconciled with a ring-opening mechanism for alkene
replacement in the Os2(CO)8(alkene)
system. We
have confirmed that alkene exchange with
Os(CO)4(alkene) is dissociative, in agreement
with precedent. The secondary
deuterium kinetic isotope effect (KIE) has been measured for the
replacement of C2H4 and
C2D4 in
Os2(CO)8(μ-η1,η1-C2H4)
(1) and
Os2(CO)8(μ-η1,η1-C2D4)
(1-d
4); it is 1.30(1) at 39
°C. The measured KIE is consistent with a
ring-opening associative mechanism for alkene exchange (mechanism II in
the previous paper).
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