New synthesis of meso-free-[14]triphyrin(2.1.1) by McMurry coupling and its derivatization to Mn(i) and Re(i) complexes

Abstract

The metal-free and meso-free [14]triphyrin(2.1.1) compound was successfully prepared based on the intramolecular McMurry coupling reaction of diformyl-tripyrrane in 16% yield, and was converted to the bowl-shaped Mn(I)(TriP)(CO)(3) and Re(I)(TriP)(CO)(3).

Structure Modification and Spectroscopic Properties of Artificial Porphyrinoids

“…A new synthetic strategy for meso ‐free [14]triphyrin(2.1.1) was reported, in which diformyltripyrrane 17 underwent intramolecular McMurry coupling to produce intermediate 18 , which subsequently gave triphyrin 19 by oxidation with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) with a total yield of 16 % (Scheme ) 23. The intense B‐like peak appeared at 336 nm, and the broad weaker Q‐like peaks appeared at 470 and 550 nm.…”

“…They are 20–34 nm blue‐shifted relative to those of meso aryl‐substituted [14]tiphyrin(2.1.1) 11 16. Upon coordination with low valent metal ions, such as Re(I) and Ru(I) for 15 and Mn(I) and Re(I) for 19 , the original near‐planar triphyrin ligands adopted domed or bowl‐shaped conformations with metal ions located above the plane determined by the three inner nitrogen atoms (Scheme ) 22–23. These metal complexes showed blue‐shifted and less intense absorption bands relative to metal‐free triphyrins.…”

Shaping a Porphyrinoid Frame by Heteroatoms Extrusion: Formation of an Expanded [22]Triphyrin(6.6.0)

“…The unique boron‐free triphyrin(1.1.1) has been constructed by the replacement of one pyrrole with a pyridine ring, yielding subpyriporphyrin in a free base form, however of unexplored coordination chemistry potential. Alternatively, an additional −CH= unit may expand the triphyrin(1.1.1) skeleton at one meso bridge, generating another subporphyrin homologue, namely, triphyrin(2.1.1), readily available as a free ligand in various substitution patterns . The high‐yield triphyrin(2.1.1) syntheses gave an impetus to the coordination chemistry studies of this 14 π‐electron aromatic macrocycle, which serves as a monoanionic ligand.…”

Synthesis of [14]Oxatriphyrins(2.1.1) and Their Transformation into Ethane‐Bridged Oxatripyrrins by Boron Complexation

“…[6,7] Commonly, triphyrins are known as subphthalocyanines and subporphyrins. Thus, [14]triphyrins(2.1.1) are available as monoanionic ligands and can be converted into diverse metal complexes, [8][9][10][11][12][13][14][15][16][17] as distinct from subphthalo cyanines and subporphyrins. We and others have developed the chemistry of [14]triphyrin(2.1.1), which has a relatively planar structure with 14π-electron aromaticity and can be isolated as a free base.…”

“…[23][24][25][26][27] To date, three synthetic methods have been established for preparing the triphyrin framework: 1) The modified Lindsey method, [8,14] 2) the intramolecular McMurry coupling method, [9] and 3) the [2+1] condensation method. [23][24][25][26][27] To date, three synthetic methods have been established for preparing the triphyrin framework: 1) The modified Lindsey method, [8,14] 2) the intramolecular McMurry coupling method, [9] and 3) the [2+1] condensation method.…”