Influence of Aryl Substituents on the Alignment of Ligands in the Dirhodium Tetrakis(1,2,2‐Triarylcyclopropane‐ carboxylate) Catalysts

Computational studies revealed that dirhodium tetrakis(1,2,2‐triarylcyclopropanecarboxylate) (Rh 2 (TPCP) 4 ) catalysts adopt distinctive high symmetry orientations, which are dependent on the nature of the aryl substitution pattern. The parent catalyst, Rh 2 (TPCP) 4 , and those with a p ‐substituent at the C1 aryl, such as Rh 2 ( p ‐BrTPCP) 4 and Rh 2 ( p ‐PhTPCP) 4 , adopt a C 2 ‐symmetric structure. Rh 2 (3,5‐di( p ‐ t BuC 6 H 4 )TPCP) 4 , 3,5‐disubstituted at the C1 aryl, adopts a D 2 ‐symmetric structure, whereas catalysts with an o ‐substituent at the C1 aryl, such as Rh 2 ( o ‐Cl‐5‐BrTPCP) 4, adopt a C 4 ‐symmetric structure.