Erheblich erleichterte Ring-Oxidation an Cer(IV)-bisporphyrinaten mit Doppeldeckerstruktur

Abstract

In der Tat gelingt die Oxidation priiparativ durch Umsetzung der Ce'"-Doppeldecker Ce(TTP)2 rnit dem Hexachloroantimonat des Phenoxathiin-Radikalkation~~'] in 1,2-Dichlorethan (DCE) gemllj Gleichung (c):

A Bevel‐Gear‐Shaped Rotor Bearing a Double‐Decker Porphyrin Complex

“…An intrinsic feature of LaDD is that its rotational activity can be altered. In LaDD, seven of the eight pyrrole nitrogen atoms in the two porphyrin units are coordinated to the La III atom and one nitrogen atom remains uncoordinated 16. Addition of base to LaDD induces dissociation of the uncoordinated pyrrole NH proton (to form an N − group); upon deprotonation, the value of λ max of the Soret band of LaDD shifts to shorter wavelength with a hyperchromic effect, and the coalescence temperature ( T c ) of the porphyrin rotation in LaDD increases (i.e., the rotational oscillation frequency decreases) 9e.…”

Sandwich-type heteroleptic phthalocyaninato and porphyrinato metal complexes

“…But for Ln = La, the protonated LaH(OEP)(TPP) has been isolated instead, along with a small amount of La 2 (OEP) 2 (TPP). 16 The half-sandwich compounds Ln(TPP)(acac) (Ln = Sm, 17 Eu, 15 Dy, 18 Yb, 18 Lu 19 ) also react with Li 2 (OEP) leading to the isolation of Eu(OEP)(TPP) or LnH(OEP)(TPP) (Ln = Sm, Dy, Yb, Lu). The latter species (for Ln = Sm, Lu) undergo deprotonation in basic solvents such as DMF and pyridine to form the corresponding anions [Ln(OEP)(TPP)] 2 .…”

Zirconium(IV) Sandwich Complexes of Porphyrins and Tetraazaporphyrins: Synthesis, Structure, and Nonlinear Optical Properties

“…Complexes in which the two macrocycles are the same − (homo-sandwiches) and different − (mixed-sandwiches) have been synthesized. Previously reported mixed sandwiches have been prepared using ligands having a great deal of structural variation but little electronic variation: octaethylporphyrin (OEP), tetraphenylporphyrin (TPP), and phthalocyanine (Pc) are very different structurally, but the redox potentials of Pc and TPP complexes are only 150−250 mV more positive than those of OEP complexes …”