Developments in the metal chemistry of N-confused porphyrin

A Facile Palladium‐Mediated Contraction of Benzene to Cyclopentadiene: Transformations of Palladium(II) p‐Benziporphyrin

“…[10] Porphyrinoids (including carbaporphyrinoids) provide a unique macrocyclic platform that is suitable for exploring organometallic chemistry confined to a particular macrocyclic environment. [11][12][13][14][15] Often CÀH or CÀC bonds are held close to the metal center, thus enforcing an unusual coordination geometry and unique reactivity. Herein we report the contraction of the benzene ring embedded in palladium(II) p-benziporphyrin 1.…”

Helical Bis(N‐Confused Porphyrins) with Subunits Fused by Double Orthometalation with Platinum: Adaptability of an Apparently Rigid System

“…

Modifications of the interior or periphery of porphyrins allow major alteration or fine tuning of the properties of the system, such as cation-or anion-binding ability, redox potential, absorption, emission, as well as many other properties. [8] In the readily obtainable bis(N-confused porphyrin) 2, [9] a cis-oriented system of two external nitrogen atoms can

Among the covalently [1] and coordinately [2] linked oligomers, the most attractive class is constituted by the systems in which the subunits are directly linked.…”

“…[4] The external nitrogen atom of the confused pyrrole in N-confused porphyrin (NCP) 1 [5] and some of its derivatives [6] and complexes [7] can act as a donor site. [8] In the readily obtainable bis(N-confused porphyrin) 2, [9] a cis-oriented system of two external nitrogen atoms can…”

Ruthenium N‐Confused Porphyrins: Selective Reactivity for Ambident 2‐Heteroatom‐Substituted Pyridines Serving as Axial Ligands

“…Finally, the catalytic activity of these ruthenium complexes was demonstrated through the styrene oxidation reactions. As a result, the ruthenium(II) NCP complex bearing a 2-thiopyridine moiety, together with aqueous H 2 O 2 as an oxidant showed the highest selectivity for benzaldehyde (benzaldehyde/styrene oxide = 20 : 1).As a porphyrin isomer and a type of carbaporphyrin, Nconfused porphyrin (NCP) [1] has attracted significant attention since its discovery [2] owing to its peculiar structure and properties, which differ largely from those of porphyrin. Unlike porphyrin with its four pyrrolic nitrogen atoms (NNNN) in the core, NCP provides a unique NNNC coordination environment owing to the presence of an inverted (confused) pyrrole ring in the macrocyclic framework.…”

“…As a porphyrin isomer and a type of carbaporphyrin, Nconfused porphyrin (NCP) [1] has attracted significant attention since its discovery [2] owing to its peculiar structure and properties, which differ largely from those of porphyrin. Unlike porphyrin with its four pyrrolic nitrogen atoms (NNNN) in the core, NCP provides a unique NNNC coordination environment owing to the presence of an inverted (confused) pyrrole ring in the macrocyclic framework.…”