Premium
β,β′‐Bipyrrole Fusion‐Driven cis ‐Bimetallic Complexation in Isomeric Porphyrin
Author(s) -
Sarma Tridib,
Kumar B. Sathish,
Panda Pradeepta K.
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201508409
Subject(s) - bimetallic strip , chemistry , palladium , natural bond orbital , metal , porphyrin , aromaticity , ligand (biochemistry) , crystallography , ring (chemistry) , photochemistry , stereochemistry , computational chemistry , density functional theory , molecule , organic chemistry , catalysis , biochemistry , receptor
An unprecedented cis‐bimetallic complex of dinaphthoporphycene (DNP), namely [Pd 2 (μ‐DNP)(μ‐OAc) 2 ], is reported. The most striking feature of this complex is that two palladiums coordinate to the macrocycle on the same side and are closely held together (PdPd: 2.67 Å) by two bridging acetate ligands exhibiting significant metal–metal bonding interaction (bond order 0.18 evaluated by NBO analysis). Interestingly, replacing acetate with acetylacetonate (acac) could stabilize an unusual mono‐palladium complex of DNP, where Pd coordinates unsymmetrically to two ring Ns above the macrocyclic plane, as well as coordinating with two Os of the acac ligand. Remarkably, the rigid DNP core displays enhanced complexation induced aromaticity (as per NICS and HOMA analysis), despite undergoing severe core deformation during complexation with metal ion(s) as noticed from their solid‐state structures.