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

摘要

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 ap-substituent at the C1 aryl, such as Rh-2(p-BrTPCP)(4)and Rh-2(p-PhTPCP)(4), adopt aC(2)-symmetric structure. Rh-2(3,5-di(p-(BuC6H4)-Bu-t)TPCP)(4), 3,5-disubstituted at the C1 aryl, adopts aD(2)-symmetric structure, whereas catalysts with ano-substituent at the C1 aryl, such as Rh-2(o-Cl-5-BrTPCP)(4,)adopt aC(4)-symmetric structure.