Cerium(IV) bis(octaethylporphyrinate) and dicerium(III) tris(octaethylporphyrinate): parents of a new family of lanthanoid double-decker and triple-decker molecules

Journal Article · Wed Jun 25 04:00:00 EDT 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00273a018· OSTI ID:5658811

Buchler, J W; De Cian, A; Fischer, J; Kihn-Botulinski, M; Paulus, H; Weiss, R

The synthesis, spectral characterization, and crystal structure determination of novel lanthanoid porphyrins, i.e., cerium(IV) bis(octaethylporphyrinate) (Ce(OEP)/sub 2/) and dicerium(III) tris(octaethylporphyrinate)(Ce/sub 2/(OEP)/sub 3/), are described. Synthesis is achieved by prolonged boiling of cerium(III) acetylacetonate (Ce(acac)/sub 3/) and octaethylporphyrin (H/sub 2/(OEP)) in 1,2,4-trichlorobenzene, C/sub 6/H/sub 3/Cl/sub 3/, followed by chromatography on basic alumina. Solutions of reddish-brown, diamagnetic Ce(OEP)/sub 2/ slowly decompose, depositing scarcely soluble, brown paramagnetic Ce/sub 2/(OEP)/sub 3/. The solution structures are deduced from /sup 1/H resonance spectra, and the solid-state structures are proved by X-ray crystallography of monoclinic Ce(OEP)/sub 2/ (P2/sup 1//n) and monoclinic (P2/sub 1//c) or tetragonal (I 4) modifications of bis(trichlorobenzene) or tetrakis(benzene) solvates of Ce/sub 2/(OEP)/sub 3/. The bisporphyrinate is a double-decker while the trisporphyrinates are triple-decker molecules. The cerium ions appear in an approximate square-antiprismatic geometry with Ce-N distances of 2.48 A for the Ce/sup IV/ and of about 2.50 A (external porphyrinate) and 2.75 A (internal porphyrinate) for the Ce/sup III/ sandwich systems. The external porphyrinates are bent away from the cerium ions in a saucer-like shape, whereas the internal porphyrinate is planar. The two mean planes of the 24 core atoms of the individual porphyrin rings lie 3.40 or 3.54 A away from each other in the double-decker or triple-decker, respectively.

• Research Organization: Technische Hochschule, Darmstadt, West Germany
• OSTI ID: 5658811
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:13; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
BOND ANGLE
BOND LENGTHS
CARBOXYLIC ACIDS
CERIUM COMPLEXES
CHEMICAL PREPARATION
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
DIMENSIONS
EXPERIMENTAL DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
INFRARED SPECTRA
LATTICE PARAMETERS
LENGTH
MASS SPECTRA
NMR SPECTRA
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PORPHYRINS
RARE EARTH COMPLEXES
SCATTERING
SPACE GROUPS
SPECTRA
SYNTHESIS
ULTRAVIOLET SPECTRA
VISIBLE SPECTRA
X-RAY DIFFRACTION