Corroles with Group 15 Ions. 2. Synthesis and Characterization of Octaethylcorroles Containing a Phosphorus Central Atom

The synthesis, spectroscopic characterization, and electrochemistry of five new phosphorus corroles are reported. The investigated complexes contain alkyl, aryl, oxo, or hydrido axial ligands and are represented as (OEC)P(H)2, (OEC)P(CH3)2, (OEC)P(C6H5)2, (OEC)P=O, and [(OEC)P(CH3)]+ClO4-, where OEC is the trianion of octaethylcorrole. The products of electrooxidation and/or electroreduction were also characterized by UV-vis and ESR spectroscopy. Correlations are shown to exist between reversible half-wave potentials for the first oxidation and first reduction of each compound and the combined electronegativity of the central ion and the axial ligand(s). The electrochemical HOMO-LUMO gap, d…

Structure and fluxional behaviour of heptaleneirontricarbonyl and heptalenebis (Irontricarbonyl)

Abstract The synthesis of heptaleneirontricarbonyl ( 4 ) is described. The structures of 4 and of the closely related heptalenebis(irontricarbonyl) ( 3 ) are elucidated by NMR spectroscopy ( 1H and 13C) and by X-ray crystallography. Compounds 3 and 4 are shown by dynamic NMR to undergo an isodynamic 1 ,2-migration of the Fe(CO3)-groups as well as a carbonyl scrambling. The relevant kinetic data allow for a mechanistic discussion of the dynamics and a comparison with other irontricarbonyl complexes.

New Porphycene Ligands: Octaethyl- and Etioporphycene(OEPc and EtioPc)—Tetra- and Pentacoordinated Zinc Complexes of OEPc

syn-1,6-imino-8,13-oxido[14]annulene

Abstract syn -1,6-Imino-8,13-oxido[14]annulene (1) , an aromatic annulene featuring closely spaced NH and O-bridges, has been synthesized. Contrary to expectation, NH ⋯ O hydrogen bonding in I does not profit from the proximity of the functionalities noticeably.

ChemInform Abstract: New Porphycene Ligands: Octaethyl- and Etioporphycene (OEPc and EtioPc) - Tetra- and Pentacoordinated Zinc Complexes of OEPc.

Doubly charged ions of bridged [4n] annulenes. An evaluation of diatropic ring current effects.

Abstract [4n]Annulenes are transformed into doubly charged ions (dianion, dication) and characterized NMR spectroscopically. The diatropic character of the ionic (4n+2)π-systems is studied as a function of the number of π-electrons.