Abstract
Hammett correlation experiments were used to determine the influence of dirhodium(II,II) paddlewheel complexes with tethered, axially coordinated ligands (TACLs) on the selectivity of rhodium carbenoids in competitive cyclopropanation reactions. The results suggest that dirhodium(II,II) paddlewheel complexes with TACLs are less sensitive to changes in electronics and reduce selectivity in cyclopropanation reactions with acceptor-substituted rhodium carbenoids. Also, Hammett plots with aryl diazoacetates resulted in a nonlinear downward curvature, suggesting a change in the rate-limiting step of the carbene transfer reaction.
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