Stereoelectronic control of the regioselectivity of both electrophilic and nucleophilic substitution of η⁶-(1,1-dimethylindane) tricarbonylchromium(0)

η⁶-(1,1-Dimethylindane)tricarbonylchromium(0) reacts with the nucleophile LiC(Me)₂CN at C-5, a position eclipsed by a metal carbonyl bond in the preferred conformation of the molecule, and at C-6 and C-4, positions not eclipsed by metal carbonyl bonds with the electrophile MeCO ⁺, confirming that stereoelectronic effects can dominate the regioselectivity of substitution of arenetricarbonylchromium complexes where the tricarbonylchromium unit adopts a highly preferred conformation.