Claude F. Bernasconi and Aquiles E. Leyes
A kinetic study of the hydrolysis of the title compound, 6, in 50%
acetonitrile–50% water (v/v) at 25 °C is reported. The
organic products are 2-hydroxytetrahydrofuran in equilibrium with small
amounts of 4-hydroxybutanal. There are two possible mechanisms that can
account for the hydrolysis. (i) Rate limiting reaction of the
conjugate anion of 6 (6-) with water, buffer acids and
H3O+, followed by (CO)5Cr catalyzed
hydrolysis of the resulting 2,3-dihydrofuran. (ii) Ring opening
of 6 through nucleophilic substitution on the carbene carbon by
OH-, water or by buffer base catalyzed water attack,
followed by breakdown of the intermediate substitution product into
final hydrolysis products. Kinetic solvent isotope effects can be
interpreted by either mechanism. Based on more conclusive isotope effect
experiments in the hydrolysis of
(CO)5CrC(OR′)CH3
(R′ = CH3 or
CH3CH3) and
(CO)5Cr
C(OMe)CH2Ph reported earlier, the
first mechanism is preferred by reason of analogy, at least in basic
solution. In acidic solution the mechanistic ambiguity could not be
resolved, not even for (CO)5Cr
C(OMe)CH3
which was reinvestigated in HCl and DCl solutions.