Metal–Ligand Bonding Situation in Ruthenophanes Containing Multibridged Cyclophanes

Cation−π interactions in a set of ruthenophanes [Ru­(η⁶-C_<i>n</i>H_<i>n</i>)­(NH₃)₃]²⁺ (<i>n</i> = 16, 18, 20, 22, and 24) (<b>1</b>–<b>9</b>), containing multibridged cyclophanes as ligands, including [2.2]­paracyclophane and its multibridged analogs, [2_<i>n</i>]­cyclophanes, are analyzed in terms of SAPT0/TZP and Su–Li EDA analyses. The calculations reveal that the coordination with cation [Ru­(NH₃)₃]²⁺ affects the structures of [2_<i>n</i>]­ciclophane ligands, mainly the planarity of the coordinating ring. The EDA results show that the gradual addition of ethano bridges in [2_<i>n</i>]­cyclophanes tends to strengthen the cation−π interaction between [Ru­(NH₃)₃]²⁺ and [2_<i>n</i>]­cyclophane. Both Su–Li EDA and SAPT0 are in line, suggesting that the cation−π interactions present a predominant covalent character in complexes <b>1</b>–<b>9</b>

Metal–Ligand Bonding Situation in Ruthenophanes Containing Multibridged Cyclophanes

Cation−π interactions in a set of ruthenophanes [Ru­(η⁶-C_<i>n</i>H_<i>n</i>)­(NH₃)₃]²⁺ (<i>n</i> = 16, 18, 20, 22, and 24) (<b>1</b>–<b>9</b>), containing multibridged cyclophanes as ligands, including [2.2]­paracyclophane and its multibridged analogs, [2_<i>n</i>]­cyclophanes, are analyzed in terms of SAPT0/TZP and Su–Li EDA analyses. The calculations reveal that the coordination with cation [Ru­(NH₃)₃]²⁺ affects the structures of [2_<i>n</i>]­ciclophane ligands, mainly the planarity of the coordinating ring. The EDA results show that the gradual addition of ethano bridges in [2_<i>n</i>]­cyclophanes tends to strengthen the cation−π interaction between [Ru­(NH₃)₃]²⁺ and [2_<i>n</i>]­cyclophane. Both Su–Li EDA and SAPT0 are in line, suggesting that the cation−π interactions present a predominant covalent character in complexes <b>1</b>–<b>9</b>