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Experimental constraints on the relationship between the rate-constant ratios kb/ka and kc/ka. The dashed lines show the values required for these two ratios if the Wolff rearrangement of carbene 3 were to occur as expected by statistical kinetic models (i.e., with f = 0.5). The horizontal and vertical red lines, respectively, show the independently assessed values of kb/ka and kc/ka from coupled-cluster calculations.
