Synthesis and Characterization of N-Fused Porphyrin Rhodium Complex with an Isomerized Cyclooctadiene Ligand

The Intracavity Extension of 28-Hetero-2,7-naphthiporphyrins in Reactions with Alkylamines

“…In 4-Se , the pyrrole C nitrogen atom was involved in forming a bridge. Similar reactivity of the pyrrole of the macrocycle was previously demonstrated for N-fused porphyrins and carba- and heteroporphyrinoids. − The tetrahydroazepine ring adopted a boatlike conformation enforcing the endo -position of a hydrogen atom at the tetrahedral C8. The C30–C31 distance of 1.344(5) Å indicated a double-bond character, consistent with the valence structure depicted in Scheme .…”

Creation from Confusion and Fusion in the Porphyrin World─The Last Three Decades of N-Confused Porphyrinoid Chemistry

“…When 21-Br-NFP 48 was treated with [RhCl-(COD)] 2 , the NFP rhodium(I) complex 322a was obtained in 16% yield, where the COD ligand was isomerized into a 1-κ-4,5,6-η 3 -C 8 H 12 ligand (Scheme 129). 325 In a solution, rotation of the COD ligand in 322a was observed, which might give its isomer 322b. In a similar reaction of NFTPP with [Ir(OMe)-(COD)] 2 under argon atmosphere, an equimolar amount of NFP iridium(III) complexes 323a and 323b was obtained in 61% combined yield (Scheme 130).…”

Marriage of an N-Fused and a Regular Porphyrin in a Cofacial Ligand System

“…Complexes of NFPs with various atomic cations can be grouped into “in-plane” and “atop” coordination types. Due to the tri-pentacyclic rings, only ions with comparatively small ionic radii can be incorporated into the NFP plane, as is the case for the B­(III) complexes reported by Latos-Grażyński et al By contrast, P­(V), Mn­(I), W­(VI), Re­(I), , Rh­(I), and Ir­(I) all coordinate above the NFPs’ plane. This provides enough space for various ancillary ligandsa feature which cannot be realized in regular, in-plane porphyrin–metal complexes of 3d metals.…”