Macrocycle- and metal-centered reduction of metal tetraphenylporphyrins where the metal is copper(ii), nickel(ii) and iron(ii)

Abstract

Reduction of metal(II) tetraphenylporphyrins, where metal(II) is copper, nickel or iron, has been performed in toluene solution using cesium anthracenide as a reductant in the presence of cryptand. Crystalline salts...

Crystalline paramagnetic supramolecular 2D-polymer of the tetra(4-pyridyl)porphyrin and terbium(iii) complex

“…The asymmetric unit of 1 contains one whole n-hexane molecule, and an n-hexane molecule in another position has 0.417 (16) occupancy. One tert-butyl substituent of Tb(TMHD) 3 is disordered between two orientations with 0.517(17)/0.483 (17) occupancies. The hydrogen atoms in the center of H 2 T(4-Py)P are disordered between four positions with 0.350(3)/0.650(3)/ 0.350(3)/0.650(3) occupancies, and total occupancy is 2 as expected for neutral H 2 T(4-Py)P. Crystal data for 1:…”

“…To date only a series of crystalline compounds based on reduced metallo-or free-base porphyrins such as tetraphenylporphyrin (TPP), tetrakis( pentafluorophenyl)porphyrin {T(F 5 Ph)P} and tetra(4-pyridyl)porphyrin {T(4-Py)P} were obtained and studied. [15][16][17][18][19] Preparation of supramolecular assemblies based on reduced paramagnetic porphyrin macrocycles and their metal complexes is of particular interest. It is known, for example, that magnetic interactions between the paramagnetic metal atoms in coordination complexes can be significantly enhanced by the introduction of an unpaired electron to a ligand.…”

Dynamic ion-pairing behaviour of “naked” aluminyls: Facile activation of H2

“…Single crystal X-ray diffraction data [14] disclose both [(crypt)Cs)] ). [4c, 4d] This abstraction of Cs from the crypt ligand and the formation of Cs•••anion interactions has also been observed to be key in other multiply-charged negative ions [16] and allowing charge-disproportionation processes between counterions. [17] Dissolving isolated Å) that is close to the sum of the covalent radii (åcov = 3.65 Å for Cs-Al), [15] and a Cs•••π(arene) contact of ~ 3.62 Å.…”

"Contacted" vs "separated" aluminyls: Dynamic alkali metal effects in H2 activation

“…). [3c, 3d] This abstraction of Cs from the crypt ligand and the formation of Cs•••anion interactions have also been observed to be key in other multiply-charged negative ions, [17] allowing charge-disproportionation processes between counterions. [18] Dissolving a small sample of crystals of that is close to the sum of the covalent radii (åcov = 3.65 Å for Cs-Al), [16] and a Cs•••π(arene) contact of 3.62 Å.…”